A structure is composed of the domain, constants, relation symbols, and function symbols. I understand all of the ingredients of a structure immediately except for the constants. The definition in my book (A Shorter Model Theory) is
A set of elements of $A$ called constant elements, each of which is named by one or more constants. If $c$ is a constant, we write $c^A$ for the constant element named by $c$.
An example of a structure with constants is
$$\langle \mathbb{R}, +, -, \cdot, 0,1, \le \rangle$$
I understand that $0$ and $1$ are special because they are the identity elements for addition and multiplication, respectively, but why are they the constants, and in what sense do we need to specify them? I understand that I get a totally different structure if I where to use $<$ instead of $\le$, but I don't see what is so special about the constants. Why not have a structure of the following type:
$$\langle \mathbb{R}, +, -, \cdot, \frac{1}{2},\pi, \le \rangle$$
Is this different and if so, in what sense? Viewed as a group $\mathbb{R}$ has many choices of elements but only one identity element so I can make sense of specifying the identity element when talking about a group, but in what sense are the symbols related when we write out the structure (or signature)?
I think the real meat of your question is when you write:
The answer is: yes, they are very different - specifically, they are not isomorphic. Let me describe a bit how the choice of (interpretations of) constants (symbols) in particular can affect the isomorphism type of a structure; I'll use simpler examples, but it should be clear how to address your specific example the same way.
Constants - or rather, the interpretations of constant symbols - can be anything you want (that is, any elements of the structure in question), and precisely how a constant symbol is interpreted affects the isomorphism type of the structure.
Specifically, let's look at the language $L=\{\color{red}{ +}, \color{red}{ \times}, \color{red}{ c}\}$ for simplicity where $\color{red}{ +},\color{red}{ \times}$ are binary functions and $\color{red}{ c}$ is a constant symbol (and for clarity I'll use red text for symbols, and usual black text for actual functions/elements - that is, for the interpretations of the symbols). Let's consider two structures:
$\mathcal{A}=(\mathbb{R}; \color{red}{ +}^\mathcal{A}=+, \color{red}{ \times}^\mathcal{A}=\times, \color{red}{ c}^\mathcal{A}=0)$
$\mathcal{B}=(\mathbb{R}; \color{red}{ +}^\mathcal{A}=+, \color{red}{ \times}^\mathcal{A}=\times, \color{red}{ c}^\mathcal{A}=17)$.
(Note that $17$ is a really silly choice of interpretation for $\color{red}{ c}$ - but that's fine! There's no rule on what sort of element of the structure a constant symbol can be interpreted as - we can use a constant to denote any element whatsoever. We could equally well have chosen $\pi$ or $\sqrt{2}$.)
There is a natural bijection between these two structures, namely the identity $id: r\mapsto r$.
Is $id$ an isomorphism?
Well, to be an isomorphism is to preserve all "basic" formulas (and be bijective); in this case, the "basic" formulas are:
$x\color{red}{+}y=z$.
$x\color{red}{\times}y=z$.
$x=\color{red}{ c}$.
It's easy to see that the last of these is not preserved by $id$: we have $$\mbox{$\mathcal{A}\models 0=\color{red}{ c}^\mathcal{A}\quad$ but $\quad\mathcal{B}\models\neg id(0)=\color{red}{ c}^\mathcal{B}$.}$$
This means that $id$ is not an isomorphism.
Now, you might object that $\mathcal{A}$ and $\mathcal{B}$ are "really" the same, the only difference is in the silly choice of evaluation of $\color{red}{ c}$. But isomorphism is a precise notion; it doesn't take into account whether or not we think part of the structure is "silly." That said, here are a couple relevant facts:
$\mathcal{A}$ and $\mathcal{B}$ do have isomorphic reducts (when we forget the constant symbol $\color{red}{ c}$): letting $L_0=\{\color{red}{ +}, \color{red}{ \times}\}$, $\mathcal{A}$ and $\mathcal{B}$ have reducts $\mathcal{A}_0=(\mathbb{R}; \color{red}{ +}^\mathcal{A}=+, \color{red}{ \times}^\mathcal{A}=\times)$ and $\mathcal{B}_0=(\mathbb{R}; \color{red}{ +}^\mathcal{A}=+, \color{red}{ \times}^\mathcal{A}=\times)$. These are obviously isomorphic - in fact, they are literally the same structure.
Moreover, in a precise sense $\mathcal{A}$ can be "recovered from" $\mathcal{A}_0$ and $\mathcal{B}$ can be "recovered from" $\mathcal{B}_0$ - that is, $0=\color{red}{ c}^\mathcal{A}$ is definable in $\mathcal{A}_0$ and $17=\color{red}{ c}^\mathcal{B}$ is definable in $\mathcal{B}_0$ (exercise - note that this is not true for all possible choices of constants, e.g. interpreting $\color{red}{ c}$ as $\pi$).
So $\mathcal{A}$ and $\mathcal{B}$ are "equivalent" in a certain sense (namely they are bi-interpretable). But this isn't isomorphism.
Here's a further observation which I think will help clarify just how "rigid" the notion of isomorphism is:
Look at the language $S=\{\color{red}{ c_0}, \color{red}{ c_1}\}$ consisting only of two constant symbols, and think about the structures $$\mathcal{C}=(\mathbb{R}; \color{red}{ c_0}^\mathcal{C}=0, \color{red}{ c_1}^\mathcal{C}=1)\quad\mbox{ and }\quad \mathcal{D}=(\mathbb{R}; \color{red}{ c_0}^\mathcal{C}=1, \color{red}{ c_1}^\mathcal{C}=0).$$ Then - perhaps surprisingly - the identity map $id$ is not an isomorphism between them since
It doesn't "send $\color{red}{c_0}$ to $\color{red}{c_0}$" - we have $id(\color{red}{c_0}^\mathcal{C})=id(0)=0\color{green}{\not=}1=\color{red}{c_0}^\mathcal{D}$.
It doesn't "send $\color{red}{c_1}$ to $\color{red}{c_1}$" - we have $id(\color{red}{c_1}^\mathcal{C})=id(1)=1\color{green}{\not=}0=\color{red}{c_1}^\mathcal{D}$.
(Crucial inequalities highlighted in green.)
Being an isomorphism is a really really strict property: you have to really preserve all the "basic facts" about the structure exactly as written.
(Incidentally, $\mathcal{C}$ and $\mathcal{D}$ above are isomorphic e.g. via the map swapping $0$ and $1$ and leaving everything else unmoved - as an exercise, check that this is the case and then cook up an example of two structures, which differ only in "swapping" a pair of constant symbols, which are not isomorphic at all.)