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Russ, the requirement is only unreasonable if I restrict my knowledge of the CW complex to the degrees of the attaching maps as indicated in the original question. Thanks for the link to Barmak's paper.
Josh: presentation groups are 2 dimensional, see (en.wikipedia.org/wiki/Presentation_complex) and you can build your own examples from finitely presented groups. Qiaochu: I don't need an explicit chain map, just isomorphic homology.
Igor: in this case, efficiency is not very important because the input has small size, both in terms of cell count and also in terms of the degrees of attaching maps.
Igor, I am looking at presentation complexes of some small groups and of course the words in many relations contain exponents that are not $\pm 1$. I can add more detail if necessary, but I was trying to keep the question concise.
I like the spirit of this question: visual intuition is often crucial in topology and geometry, and I would certainly benefit from good answers. However, I think it could be much improved if you focus on a question of the type: "are there good visual interpretations of homotopy theoretic constructions such as (blah), for instance by attaching cells?" rather than ask people whether they would personally find such constructions useful.
Of course, I have just realized that the cohomology cup product construction requires the Kunneth map also, since the cohomology of the product is not the product of the cohomology. I'm not sure how this translates into the "homology of Lie groups" setting though, so I will leave the question as it stands.