I know that the members of the natural numbers are either $0$ or $S(n)$,for some $n\in\mathbb{N}$. So if I proceed from here and define "addition" as $+:\mathbb{N}\times\mathbb{N}\rightarrow\mathbb{N}$ such that:-
$m+0=0$ and $m+S(n)=S(m+n)$ then I can conclude that $2n=S(m)+S(m)$ . Now what I want to say is that the sum of two equal natural numbers cannot be $1$ using Peano's axiom. This is what I cannot prove as I am having a lot of confusion as to where and how to start. These formalisms are new to me and my english is not very strong as to understand all of the subtelties . Can anyone help me out with this?. If someone proceeds without using the $+$ then also it is fine by me. I just want to know how a proof would look like. That would help me in developing a framework as to how I should prove such things if I encounter them in the future.

The first question is: How can you express that a number is even using the peano axioms? By definition, we say that $0$ is even. We recursively say that a number $y$ is even if $y$ is of the form $y=S(S(x))$ where $x$ was already established to be an even number.
With the above in mind, how can we show that $1$ is not even? Clearly, $1\neq 0$ as $S(0)=1$ and of the axioms precisely states that $S(n)\neq n$. Great, so $1$ is not the even number $0$. The 'next' even number (after zero) is $2=S(S(0))$ and we know that $2\neq 1$ as $2=S(1)\neq 1$ by the same axiom. That's great but even if we keep doing this, it's not immediately clear that every even number can be attained by repeatedly applying $S(S(-))$ to zero and so on.
Note that this does not yet imply that $1$ is odd (we haven't even defined odd yet).