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The various lighting techniques are a bit hard to explain in writing without images. Generally, to make a face look slimmer you want the lighting set up so that the side of the nose facing the camera (in a 3/4 shot) is in shadow. Frontal, symmetrical poses and frontal flat lighting can make faces look fatter.
I highly recommend checking out a couple of portrait photography books from the library or ordering some of the ones recommended in Cynthia's book list on this site. Unless an artist has the luxury of working only from life, mastering portrait photography (and especially lighting) is essential, in my opinion.
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