Let's assume you have the typical axioms for Successor:
$$\forall x \ s(x) \neq 0$$
$$\forall x \forall y \ (s(x) = s(y) \to x = y)$$
and the Axiom Scheme of Induction, which states that for any formula $\varphi(x)$, we have:
$$(\varphi(0) \land \forall x (\varphi(x) \to \varphi(s(x))) \to \forall x \ \varphi(x)$$
Then, if you add:
$$\forall x \forall y (x < y \leftrightarrow (s(x) = y \lor \exists z (y = s(z) \land x < z))) \tag{*}$$
you can prove all of the following:
$$\forall x \ x < s(x)$$
$$\forall x \ \neg x < 0$$
$$\forall x \neg \exists y (x < y \land y < s(x))$$
$$\forall x \ \neg x < x \text{ (irreflexivity)}$$
$$\forall x \forall y (s(x) < s(y) \to x < y)$$
$$\forall x \forall y \forall z ((x < y \land y < z) \to x < z) \text{ (transitivity)}$$
$$\forall x \forall y (x < y \to \neg y < x) \text{ (asymmetry)}$$
$$\forall x \forall y (x = y \lor x < y \lor y < x) \text{ (trichotomy)}$$
So, you can prove all kinds of important and elementary facts about $<$ by adding that one statement to the basic axioms about $s$.
Of course, you would define $x \leq y$ simply as $x < y \lor x = y$ to get results regarding $\leq$, including:
$$\forall x \ x \leq x \text{ (reflexivity)}$$
$$\forall x \forall y \forall z ((x \leq y \land y \leq z) \to x \leq z) \text{ (transitivity)}$$
$$\forall x \forall y (x \leq y \lor y \leq x) \text{ (totality)}$$
Also, once you do add the typical axioms for addition:
$$\forall x \ x+0=x$$
$$\forall x \forall y \ x + s(y) = s(x+y)$$
then you can derive the 'standard' definition of inequality in terms of addition:
$$\forall x \forall y (x \leq y \leftrightarrow \exists z \ x + z = y)$$
In sum: Yes, we can have an alternative definition of smaller than or inequality that allow you to prove important things about it without using the axioms of addition.