My question begins with a caveat: I sometimes spend time with topologists, but do not consider myself to be one. In particular, my apologies for any errors in what I say below — corrections are encouraged.
My impression is that manifold topologists like to consider three main categories of (finite-dimensional, paracompact, Hausdorff) manifolds, which I will call $\mathcal C^0$, $\mathrm{PL}$, and $\mathcal C^\infty$, corresponding to manifolds whose atlases have transition functions that are, respectively, homeomorphisms, piecewise-affine transformations, and diffeomorphisms. The latter two categories obvious map faithfully into the first, and a theorem of Whitehead says that every $\mathcal C^\infty$ manifold admits a unique PL structure.
These categories are not equivalent in any reasonable sense. The generalized Poincare conjecture is true in $\mathcal C^0$, true (except possibly in dimension $4$) in $\mathrm{PL}$, and false in many dimensions including $7$ in $\mathcal C^\infty$. $\mathcal C^0$ is the realm of surgery and h-cobordism. In $\mathcal C^\infty$, and in particular in $4$ dimensions, there is a powerful tool called "gauge theory", which provides the main technology used to prove examples of homeomorphic but not diffeomorphic manifolds.
By definition, gauge theory is that part of PDE that studies connections on principal $G$-bundles for Lie groups $G$. The most important gauge theories for distinguishing between the $\mathcal C^\infty$ and $\mathcal C^0$ worlds are Donaldson Theory (which studies the moduli space of $\mathrm{SU}(2)$ connections with self-dual curvature) and the conjecturally equivalent Seiberg–Witten Theory (which studies an abelian gauge field along with a matter field, and which I understand less well). Another important gauge theory that I understand much better is (three-dimensional) Chern–Simons Theory, whose PDE picks out the moduli space of flat $G$ connections; for example, counting with sign the flat $\mathrm{SU}(2)$ connections on a 3-manifold is supposed to correspond to the Casson invariant.
My impression, furthermore, has been that the categories $\mathcal C^\infty$ and $\mathrm{PL}$ are in fact quite close. There are more objects in the latter, certainly, but in fact many of the results separating $\mathcal C^0$ from $\mathcal C^\infty$ in fact separate $\mathcal C^0$ from $\mathrm{PL}$. A side version of my question is to understand in better detail the distance between $\mathcal C^\infty$ and $\mathrm{PL}$. But my main question is whether the technology of gauge theory (possibly broadly defined) can be used to separate them. A priori, the whole theory of PDE is based on smooth structures, so it would not be unreasonable, but I am not aware of examples.
Are there gauge-theoretic invariants of smooth manifolds that distinguish nondiffeomorphic but $\mathrm{PL}$-isomorphic manifolds?
Of course, a simple answer would be something like "For any $X,Y \in \mathcal C^\infty$, the inclusion $\mathcal C^\infty \hookrightarrow \mathrm{PL}$ induces a homotopy equivalence of mapping spaces $\mathcal C^\infty(X,Y) \to \mathrm{PL}(X,Y)$." This would explain the impression I have that $\mathcal C^\infty$ and $\mathrm{PL}$ are close — if it is true, it is not something I recall having been told.