Do trivial homology groups imply contractibility of a compact polyhedron?
Solution 1:
The 2-skeleton of the Poincare homology sphere, also describable as the presentation complex of the binary icosahedral group, provides a counterexample to your original question. The fundamental group is of order 120 and is perfect, which implies that that $H_1$ is trivial. You can check from the group presentation $ <s,t | s^{-3}(st)^2, t^{-5}(st)^2> $ that the second homology group is trivial as well.
Solution 2:
To sum up the comments: when Poincaré worked on the beginnings of algebraic topology, he originally thought that a space with trivial homology groups must be contractible. (More precisely, he thought that having the homology group of a 3-sphere implies being a 3-sphere.) However, he soon found a counterexample, the Poincaré homology sphere, which led him to the construction of the fundamental group.
When taking the fundamental group into account, the statement is indeed true: if a space has trivial fundamental group and trivial higher homology groups, then it must be contractible. This is a consequence of Whitehead's theorem and the Hurewicz map.
Solution 3:
(This is the deleted answer the comments refer to; it was missing the hypothesis about simple-connectedness)
Using the Hurewicz theorem, you deduce at once that such a polyhedron [Edit: if it is simply connected] has trivial homotopy groups, so that it is weakly homotopy equivalent to a point. Since it is a CW-complex, then Whitehead's theorem tells you that the polyhedron is in fact contractible.