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Comments
classification
I'd recommend you separate the DVDs from the videos because people are getting where they just want a DVD and don't want to wade through the VHS tapes. The CDs should be separated into music and audiobooks.
Put them in alphabetic order by title, or if there are a whole bunch you might try to the Dewey Decimal System to arrange subjects together. Or if that's too hard to figure out, you could go with colored dots and use a big bookstore's subject divisions.
Or hire a librarian. Grin.
Don't use Dewey or LC!
Whatever you do, don't use Dewey or LC. The best bet is alphabetical order, and signs. This is what bookshops do!
Alternative classification
You could look into ANSCR classification designed specifically for CDs (http://www.gti.net/mocolib1/music/anscr.html is a pretty good explanatory site). While I only worked briefly with it as an undergrad tech services assistant, it makes quite a bit more sense than using DDC or LCC.