One thing to keep in mind is that "provable" is always with respect to some axiomatic system, such as Peano Arithmetic, or ZFC. And when we show something is unprovable, we have to do so in a larger system and reason about our initial system.
That said, we do know roughly speaking that there are statements which are unprovable and where we cannot prove that in any reasonable system.
Consider the Turing Halting problem. This asks whether given a specific Turing Machine, whether it will halt when run on a given input tape. We know that this problem is in general unsolvable, in the strong sense that there is no Turing machine which solves the Halting problem. However, note that if a given Turing machine halts on a given tape, then there is a proof of that: simply run the machine that many steps. Suppose now that there were some general axiomatic system A where we could always either prove that whether a given Turing machine halting on a given tape was undecidable in Peano Arithmetic (or whatever your preferred system of axioms is that is strong enough to talk about Turing machines).
Then, we solve the Halting Problem, since we could encode a Turing machine M, which given another Turing machine X and an input y, alternates between steps of running X in y, and searching for a proof in A, that X halting on y is undecidable in Peano Arithmetic. By assumption, this machine will eventually either find when X halts on y, or will find a proof in A that Peano Arithmetic will not resolve the problem, which means that X must never halt on y.
Thus, we have given the existence of A, constructed a Turing machine M which can solve the Halting problem. But we know that such a machine cannot exist, so our assumption that we had such an axiomatic system must be false.
(There are some subtleties here I've brushed under the rug. I've assumed consistency of all relevant systems, and we need to be careful about what we mean by an axiomatic system. But the central ideas here are correct.)
Thanks to JoshuaZ (feel free to post the answer yourself, I will
accept it)