The OP referenced an explicit example of a transformation of the (now given) natural numbers satisfying the Peano axioms. But given the standard successor function $S: n \mapsto n+1$ on $\Bbb N$, if $\beta$ is any bijection of $\Bbb N$ then
$\quad \displaystyle \beta^{-1} \circ S \circ \beta: \Bbb N \to \Bbb N $
satisfies the Peano axioms. So, you can 'algebraically rename' the elements to get more Peano transformations. (see my answer to that explicit example).
The raison d'être for the axioms is an abstract/foundational way of 'getting to the natural numbers', and the successor function does this by 'counting off the numbers' one by one.
To answer the OP's title question - yes:
Starting with the Peano sucessor function $S: \Bbb N \to \Bbb N$ (where, at the starting gate $\Bbb N$ is an abstract set), one can define a endorelation $\rho$ on $\Bbb N$ that is a total ordering on $\Bbb N$. You are now justified in using the symbol $\le$ for the relation $\rho$. As a next foundational step you can show that $(\Bbb N, \le)$ is a well-ordered set.
The program outlined in the above paragraph can be carried out (in say the $\text{ZF}$ framework) before defining addition of the natural numbers, in contrast to the technique used in the wiki article Peano axioms and commented on by Mauro ALLEGRANZA.
The OP's foundation tag is appropriate here and they have asked a good question.