I've been looking for a way to start iTunes in fullscreen coverflow for while too.
I have iTunes on the 7-inch touchscreen in the front of my HTPC, and it looks great in fullscreen!
It's also great for my young kids, they can just tap on the screen to flip through the albums to whatever kiddie-music they'd like to hear.
Of course you have to have all the album art in place and have everything organised into albums, but if you've grown up with LP's and CD's that seems logical to me anyway.
If anyone ever finds a simple hack to start iTunes in fullscreen coverflow (for Windows 😀 ), please post it here.
Thanks!
(the attached pic shows a HTPC, just imagine iTunes on the screen ;-) )