Here is the outline of the proof, given by spaceisdarkgreen:
The models of $Th(\mathbb{N},s)$ consist of a copy of $\mathbb{N}$ and any number of copies of $\mathbb{Z}$.
For any two elements in different copies of $\mathbb{Z}$ there is an automorphism swapping them.
This means there are models of $Th(\mathbb{N},s)$ in which we cannot define an ordering (or more generally any total antisymmetric relation).
If we could define an ordering in $(\mathbb{N},s)$ the formula would define an ordering in any model of its theory.
Here is what (I think) I understand. The set $\mathbb{N}$ and the function $s$ are axiomatized by Peano axioms:
$0\in\mathbb{N}$
$\forall x\left[x\in\mathbb{N}\rightarrow s(x)\in\mathbb{N}\right]$
$\forall x\left[x\in\mathbb{N}\rightarrow\neg0=s(x)\right]$
$\forall x\forall y\left(x,y\in\mathbb{N}\rightarrow\left[x=y\leftrightarrow s(x)=s(y)\right]\right)$
$\forall K\left(0\in K\wedge\forall x\left[x\in K\rightarrow s(x)\in K\right]\rightarrow\mathbb{N}\subseteq K\right)$
Let call $\mathcal{PA}$ the set of the above statements. Then, theory $Th(\mathbb{N},s)$ is the set of all the sentences $\phi$ such that $\phi$ is a consequence of $\mathcal{PA}$:
$Th(\mathbb{N},s)=\{\phi|\mathcal{PA}\vdash\phi\}$
Models of $Th(\mathbb{N},s)$, are the structures that satisfy it's sentences. A structure has a domain $D$. The domain of a model of $Th(\mathbb{N},s)$ must contain $\mathbb{N}$, otherwise it cannot satisfy the sentences of $Th(\mathbb{N},s)$. But $D$ could contain other things also. Since $s$ must be a total function, for $x_{i}\notin\mathbb{N}$ we may also have:
• Other infinite sequences of objects with an initial element $x_{0}$: $s(x_{0})=x_{1},s(x_{1})=x_{2},...$
• Infinite sequences without an initial element: $...s(x_{i})=x_{i+1},s(x_{i+1})=x_{i+2},...$
• Circles: $s(x_{0})=x_{1},s(x_{1})=x_{2},...s(x_{n})=x_{0}$
• Finite sequences like $s(x_{0})=x_{1},s(x_{1})=x_{2},...s(x_{n})=x_{n}$
e.t.c.
Now, I'm not sure about the meaning of the expression “structure $\mathbb{N}+\mathbb{Z}+\mathbb{Z}$”, mentioned by Noah Schweber here, and either for spaceisdarkgreen's statement, “The models of $Th(\mathbb{N},s)$ consist of a copy of $\mathbb{N}$ and any number of copies of $\mathbb{Z}$”, in the comments. Surelly here “$+$” does not mean union, otherwise $\mathbb{N}+\mathbb{Z}+\mathbb{Z}=\mathbb{Z}$. And surelly $D$ can not have more than one copy of each of it's elements. So, I guess, what is meant is that, along with $\mathbb{N}$, we may also have two or more infinite sequences of the form $...s(x_{i})=x_{i+1},s(x_{i+1})=x_{i+2},...$ (which is of the same form as the sequence of integers).
If the above is correct, then, obviously, Peano axioms cannot define an ordering relation that holds for objects that are not in $\mathbb{N}$, because if we rearrange them, the sentences of $Th(\mathbb{N},s)$ will still hold. PA do not say anything about these objects anyway. But, let “$\leq$” holds only for elements of $\mathbb{N}$. What is the problem with that? And why then “the formula would define an ordering in any model of its theory”?
Or, equivalently, suppose we have the following version of first-order Peano axioms:
$\forall x\left[\neg0=s(x)\right]$
$\forall x\forall y\left[x=y\leftrightarrow s(x)=s(y)\right]$
$\forall\overline{y}\left[F(0,\overline{y})\wedge\forall x\left[F(x,\overline{y})\rightarrow F\left(s(x),\overline{y}\right)\right]\rightarrow\forall zF(z,\overline{y})\right]$, where $F$ is any formula of $k+1$ variables and $\overline{y}=y_{1},y_{2},...,y_{k}$.
From them it follows that everything is in $\mathbb{N}$ (thus, $\left|D\right|=\aleph_{0}$). Then, I can not see how we get to the conclusion.