Since the new axiom must be consistent but not hold in the standard model, it must be undecidable in $\sf PA$. But for most (all?) of the statements which we have proved undecidable in $\sf PA$, we know whether or not they hold in the standard model. We can therefore obtain a nonstandard theory by adding the statement or its negation to $\sf PA$.
So answering the question simply requires us to find the simplest statement which is known to be undecidable in $\sf PA$. Of course Gödel sentence was the first known example of such, but since then various simpler undecidable sentences have been found. The most famous are Goodstein's theorem (proved undecidable by Kirby and Paris), and the Strengthened Finite Ramsey Theorem (proved undecidable by Paris and Harrington). Both these statements are known to be true in the standard model, so we obtain a non-standard theory by adding the negation of one of them as an axiom.