Suppose I have a countable subset of the real numbers $A$. Then since it is countable there is a function $f: \mathbb N \to A$ which is bijective. This function is of course a sequence, so we can write every element $x$ of $A$ as $x_i = f(i)$. So $A= \{ x_i \mid i \in \mathbb N \}$. Of course no two $x_i$ and $x_j$ are the same.
I can now come and reorder the $x_i$'s (instead of naming the $x \in A$ as $x_i$ I can name it $x_j$) such that they are decreasing $$x_1 >x_2>\cdots. $$
(Trivial??) Question: I CAN do that right? It seems right, since any $x_i$ and $x_j$ are different, then one is bigger than the other, thus I can do this comparison with all of them and order them.
If that is the case then take as $A= \Bbb Q \cap (0,1)$ for example. What we said above is that since $A$ is countable I can write $A= \Bbb Q \cap (0,1)=\{ x_i \mid i \in \mathbb N \}$ with $x_1 >x_2>\cdots$.
But that is absurd, there is no biggest rational in $(0,1)$. It's late, what am I missing?
EDIT. Also suppose a case where there IS a biggest number such as $A=\Bbb Q \cap (0,0.9]$ where the biggest rational is $0.9$. Then we can do $ 0.9=x_1 <x_2 <x_3<\cdots$. We have no idea what $x_2$ is, but there is a rational closest to $0.9$ than all others??
" Question: I CAN do that right?"
Actually, no. The "usual" order (where $a < b$ means $b-a$ is positive) is not what is called a "well-ordering", i.e. an order in which there is always a "least" element of all subsets.
You have proven that "$<$" is not a well-ordering as $\mathbb Q \cap (0,1)$ does not have a least or greatest element. (Neither does $\mathbb Z$ or $\mathbb Q$).
!!!!BUT!!!!!, a "well-ordering" of a countable set will always exist! It just won't be "$>$".
You have actually proven that. Let $x \prec y$ mean that $f^{-1}(x) < f^{-1}(y)$. Then "$\prec$" is a well ordering and the "least" element is $x_1$.
"$\prec$" has all the properties of an "order". (Exactly one of $a \prec b$ or $b \prec a$ or $a = b$ are true; $a \prec b$ and $b \prec c \implies a \prec c$). But it doesn't mean what we think of as "bigger" and "smaller". It means nothing more or less than "comes before in a list". Which is just as valid a basis for order and "being smaller" is.
Post-script (and maybe more to the point):
Ah!... good question. The problem with this is that you never finish. You can always say "I've sorted 5 billion of them and so far $x_{1,672,453,928}$ is least and $x_{17}$ is the greatest" but then you will also have to admit "but I can not be certain that they will remain the largest and smallest... And I'll never be certain."
Try it with $\mathbb Z$". We can list all the integers in order as $0, 1,-1,2,-2, 3,-3....$.
So "$1$ is bigger than $0$ so keep $1$. $1$ is bigger than $-1$ so keep $1$. $2$ is bigger than $1$ so replace $1$ with $2$. $2$ is bigger than $-2$ so keep $2$. $3$ is biggr than $2$ so replace $2$ with $3$. $3$ is bigger tan $-3$ so..."
You see how that will never actually end and we will never actually get a largest or a smallest element.
Post-Post-Script: Notice a well ordering says all subsets will have a least element. It doesn't actually say it will have a largest element. And "comes earlier in a list" makes sets that do always have a first element but do not always have a last element.
It should be intuitive though that any axiom of definition we make for a well-ordering always having a least element could arbitrarily be make for a "perverse" ordering which always have a greatest element but not nescessarily a least. If "$\prec$" is a well-ordering, then defining "$\prec_{ident}$" as $a \prec_{ident} b \iff b \prec a$ will, of course, be a perverse ordering.
("perverse ordering" and "$\prec_{ident}$ are terms I made up and not valid mathematical terminology. I hope that was clear.)
(That's probably a lot more than you asked for.)