Does the functor $S:\mathbf{Top}\to \mathbf{sSets}$ given by $S(X)_m=Hom_{\mathbf{Top}}(\Delta^m,X)$ preserve colimits? If not, what is a counterexample?
The only things I can say are that it preserves limits because it is a right adjoint and that it preserves filtered colimits since each $\Delta^m$ is a finite CW-complex.
Does the functor $S$ preserve homotopy colimits? If not, what is a counterexample?
Again I can only say that it preserves homotopy limits as because it is a right Quillen adjoint. This Quillen adjunction with left adjoint the realization functor however is also a Quillen equivalence. I wonder if it follows already from this fact, that the right adjoint preserves homotopy colimits (and that the left adjoint preserves homotopy limits).
I find the claim about filtered colimits suspect – that question is very subtle (which is why the small object argument in $\mathbf{Top}$ has to be done carefully). Anyway, $S$ preserves coproducts, because the spaces $\Delta^n$ are all connected. Thus, $S$ preserves colimits of diagrams of discrete topological spaces. (In fact, $S$ restricts to an equivalence between discrete topological spaces and discrete simplicial sets.)
However, consider the Sierpiński space $X$, i.e. the space with one open point and one closed point. Take the coequaliser of the two maps $1 \to X$; it is $1$ again, of course. Now, $S(X)_n$ is the set of open subsets of $\Delta^n$, and the coequaliser of the two maps $S(1)_n \to S(X)_n$ simply identifies the element corresponding to $\emptyset$ with the element element corresponding to $\Delta^n$; this, of course, is still an infinite set. So we have the required example of a coequaliser not preserved by $S$.
Note, $X$ is compactly generated, so not completely pathological! But if you prefer to work in the category of compactly-generated Hausdorff spaces (say), here is another counterexample. Consider two maps $1 \to \Delta^1 \amalg \Delta^1$ whose coequaliser is $\Delta^1$. Suppose, for a contradiction, that $\mathbf{Top}(\Delta^1, -)$ preserves this coequaliser. Then the induced map $\mathbf{Top}(\Delta^1, \Delta^1 \amalg \Delta^1) \to \mathbf{Top}(\Delta^1, \Delta^1)$ must be surjective, but that is false: since $\Delta^1$ is connected, its image in $\Delta^1 \amalg \Delta^1$ must be entirely contained in one of the two copies, so there is no map $\Delta^1 \to \Delta^1 \amalg \Delta^1$ whose composite with the coequaliser map $\Delta^1 \amalg \Delta^1$ is the identity.
As for homotopy colimits: since $S$ is a homotopical equivalence (i.e. preserves weak equivalences and induces an equivalence of homotopy categories), it indeed preserves all homotopy colimits. Here I mean homotopy colimits in the sense of left derived functors.