So I'm not sure if this is possible, but I've been really liking the polypaint and spotlight options in zbrush and was hoping theres a way to do it on low poly models (under 3k tris). I haven't found a way to get it to work yet so I was hoping someone might be able to help me out or give me a definite 'no it can't be done'.
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You could, though, turn off "smt" in the smoothing options, and divide it a bunch of times until you can paint in the details you'd like, then bake them down to the low. I think that'd work the best. You could also start a texture in photoshop, and bring it into zbrush, but then I think you can only paint on it in the projection master.
Awful example with a bad UV map and nonsense texture, just to show it can be done:
i used to do this all the time until we picked up mudbox for 3d painting (much better suited for this purpose).
but yeah - if not just subdivide the model loads of times with smoothing turned off