When people say cohomology theory, I usually think of some spectrum. The reason for that is Eilenberg and Steenrod developed axioms for what a cohomology theory on the category of pairs of "nice" spaces should do. They then showed that singular cohomology satisfied these and was essentially unique. De Rham cohomology is sort of miraculous in that it is easy to see the geometry. It is staring you right in the face, these things are forms on your manifold!
The pairing you see in stokes theorem is sort of a really special case for 2 reasons. The first is the inherent geometry in De Rham cohomology. We have a geometric interpretation of what it means to be a De Rham cocycle. And by geometric I mean that for every $\alpha \in H^n_{dR} X$ where $X$ is a manifold, we understand there is some intrinsic structure on $X$ that this is detecting. This is usually not the case for other theories. We have this in $K$-theory with vector bundles and cobordism with families of manifolds, but that is it. It would be a huge deal if someone understood what $\alpha \in tmf^*X$ was supposed to be on $X$ they would win a prize (like a hug or a job or something).
The second is that singular cohomology is one of the few cohomology theories that has a formulation as the homology of some chain complex. You could ask for homology theories on spaces to really be invariants that land in chain complexes and aren't all that well defined. I am pretty sure you are just left with singular cohomology.
So let me be liberal and say that a cohomology theory should be something that satisfies the Eilenberg-Steenrod axioms, except for the dimension axiom. Lets also suppose this cohomology theory has some sort of product, then Brown representability tells us we have a ring spectrum. This is what I mean by a represented cohomology theory. So in this setting $E^*X=[X,E]$ is just the homotopy classes of maps from $X$ into the spectrum $E$, whatever that means. Similarly $E_* X$ is just homotopy classes of maps from the sphere spectrum into $X \wedge E$.
While stokes theorem is really about De Rham theory, it is really foreshadowing.
Integration of differential forms against submanifolds is really a nice model of something called the cap product, which is really only well-defined because of Stokes theorem. The cap product is like a pairing between $E^*X$ and $E_*X$. The cap product is a little more subtle, so I won't talk about it (it's not hard, just a little involved).
To answer your very specific question, there is only such a formula in singular cohomology theories because the boundary operator only makes sense in that setting.
My suggestion is that you try to pair $a \in E^*X$ and $b \in E_*X$ to get an element in $\pi_*E$ (in the case you mention $E=H\mathbb{R}$ the Eilenberg-Maclane spectrum of the reals, which represents de Rham cohomology, and the output would be a real number ... an element of $\pi_0 H \mathbb{R}$).
Let me know if you need help, but remember to use the fact that we are working with represented cohomology and homology theories and that $E$ is a ring spectrum, so it has a product map $\mu: E \wedge E \to E$.