In proof systems for classical propositional logic if one want to show that a certain formula $\psi$ is not derivable one simply shows that $\neg\psi$ can be derived (although other techniques certainly are possible). Non-derivability follows essentially from the soundness and completeness of the proof system.
Unfortunately for non-classical logics and more exotic proof systems (such as the rules underlying operational semantics) no such direct technique exists. This could be because the non-derivability of $\psi$ does not imply that $\neg\psi$ is derivable, as is the case with intuitionistic logics, or simply that no notion of negation exists.
My question is given a proof system $(\mathcal{L},\vdash)$, where $\vdash\;\subseteq\mathcal{L}^*\times\mathcal{L}$, (and presumably its semantics), what techniques exist to show non-derivability?
The proof systems of interest could include operational semantics of programming languages, Hoare logics, type systems, a non-classical logic, or inference rules for what-have-you.