This article is from the Anime Music FAQ, by Ru Igarashi with numerous contributions by others.
Some VAs seem to be committed to a singing career in addition to (or vice versa) voice acting, either in regularly performing live or releasing CDs. Others either make appearances or produce CDs in support of a show, and may do so infrequently. It's hard to say what constitutes a career, but there are quite a number of VAs that have at some point sang in addition to voice acting. The list is long enough that it shouldn't really be included here. Check Seiyuu databases, listed in the "Online Anime Music Resources" section. For example, Hitoshi Doi's Seiyuu Database is searchable and also broken down by different categories. You can also try the online CD stores (e.g. CDJapan) for specific actresses that you know (e.g. by looking it up in Hitoshi's Seiyuu database :) .
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3. Legality Issues with Anime Music
 
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