Check out these PHP scripts that access the iTunes Music Store to grab the Album Art in all it’s 600×600px glory. Also, Benjamin Morin has posted on his blog a set of scripts (script only not demo) to access the free videos like trailers and music videos from the iTunes Music store.
Hello, I am Melvin Rivera; creator of 
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For all the weirdoes like me who are obsessed in adding the artwork to every ripped album we have in our iTunes collection, THANK YOU!
I wonder if this is what the fine folks over at CoverFLow use to grab their album art?
Yes, Thank You! I wasted an entire work day on this!! And I only got to the C’s.
I really haven’t spent that much quality time with iTunes before, much less my entire music library. Got rid of duplicates and stuff I have no idea why I downloaded. Good Time Procrastination.
If you don’t care about the actual album art, you can find interesting art for your iPod at places like gig posters. You do have to do some tweaking to most of it, though.
It’s weirder being another Ben that’s obsessed with adding artwork to iTunes.