Roughly, any regularity/support class of forms that can be smoothed in a translation invariant way, without leaving the same regularity/support class, still satisfies the Poincaré lemma. An explicit example, which uses a homotopy operator similar but not identical to the one in your question, can be found in de Rham's original book (Ch.3, §15), where he discusses smoothing of currents (distributional forms) to $C^\infty$ forms.
Smoothing can be achieved by convolution with a $C^\infty$ compactly supported bump function. This smoothing map can then be show to be homotopic to the inclusion $C^\infty \subset C^k \subset \mathscr{D}'$. Thus, the de Rham cohomology in $C^k$ is isomorphic to the one in $\mathscr{D}'$, which in turn is isomorphic to the one in $C^\infty$. So the Poincaré lemma holds for all of them.
Update: This is just to write in a bit more detail what I mentioned in the comments about using the inverse Laplacian to construct a contracting homotopy. I'm essentially appealing to a variant of Hodge theory. Let $\Delta = \partial^i\partial_i$ denote the standard Laplacian on $\mathbb{R}^n$. I will denote the de Rham differential by $d$ and the co-differential by $\delta$, with explicit formulas $d[h]_{i_1\cdots i_k} = k\partial_{[i_1} h_{i_2\cdots i_k]}$ and $\delta[h]_{i_1\cdots i_k} = \partial^i h_{i i_1\cdots i_k}$. They satisfy the well-known identity $\Delta = \delta d + d\delta$, which means that $\delta$ can be thought of as a homotopy operator for the de Rham complex, inducing $\Delta$ as a null-homotopy morphism of the de Rham complex into itself.
Now, let $\Delta^{-1}$ be a Green function for $\Delta$. In other words, it is a translation invariant distribution $\Delta^{-1}(x-y)$ on $\mathbb{R}^n \times \mathbb{R}^n$ that is smooth away from the diagonal and satisfies $\Delta_x \Delta^{-1}(x-y) = \delta^n(x-y)$ (Dirac delta). We can use the formula $\Delta^{-1}[h]_{i_1\cdots i_k}(x) = \int \Delta^{-1}(x-y) h_{i_1\cdots i_k}(x)$ to make it act on forms with compact support. By translation invariance, both $\Delta$ and $\Delta^{-1}$ commute with $d$ and $\delta$.
To extend the action of $\Delta^{-1}$ on forms of non-compact support, we need a smooth compactly supported bump function $\phi$ that is identically $1$ on a neighborhood $U\ni 0$ in $\mathbb{R}^n$. Later we'll also need a partition of unity $\sum_a \chi_a = 1$ on $\mathbb{R}^n$, requiring that the supports of the $\chi_a$ are sufficiently small for each to fit into $U$ (perhaps with a safety margin) after a translation.
Let1 $\Delta^{-1}_\phi[h](x) = \int \phi(x-y) \Delta^{-1}(x-y) h(y) dy$. This operator now has the following important properties: (a) it is still translation invariant, so $d\Delta^{-1}_\phi = \Delta^{-1}_\phi d$; (b) $\Delta^{-1}_\phi[h]$ is well defined even if $h$ does not have compact support, since the defining integral now has compact support for any fixed $x$ because of the factor of $\phi(x-y)$; (c) $\Delta^{-1}_\phi[\Delta[h]] = h$ for any $h$ with sufficiently small support, which applies in particular to any argument of the form $h=\chi_a g$.
Finally, let us define the homotopy operator2 $H[h] = \Delta^{-1}_\phi[\delta h]$. It is now straight forward to verify the following identity for any $h$ with $d h = 0$:
$$
d H[h] = \Delta^{-1}_\phi[d\delta h + \delta (d h)]
= \Delta^{-1}_\phi[\Delta[h]]
= \sum_a \Delta^{-1}_\phi[\Delta[\chi_a h]]
= \sum_a \chi_a h
= h .
$$
I think this actually answers the question, provided that $\Delta^{-1}[C^k_0] \subseteq C^{k+2}$, because then $H[C^k] \subset C^{k+1}$ and the homotopy works on the complex in question. Unfortunately, I'm not sure whether that's true or not. I think it is true provided one uses some $C^{k,\alpha}$ Hölder class instead of $C^k$, though.
1 Key phrase: properly supported parametrix for the Laplacian.
2 Key phrase: properly supported parametrix for the de Rham complex.