Could one consider the structure of $\mathbb{Z_{n}}$ under addition and multiplication to simply be that of the ordinary integers, with one additional axiom - namely that $n=0$? So we would have $\mathbb{Z_{n}}=\{0,1,2,\ldots ,n-1\}$ as usual, for instance.
My question is whether this is a good way of thinking about $\mathbb{Z_{n}}$, or is there a subtlety that I've not considered that breaks it?
Nope, no subtle breakage-this works fine. It's a bit more formal to say the additional axiom is that $n$ is equivalent to $0$ and that you're calculating with representatives of equivalence classes in the resulting relation, but it amounts to the same thing when you get to actually doing modular arithmetic.