64-bit or not, there's no reason for iTunes to use 4GB RAM, so that's no benefit.
Apps can get some peformance improvements, but not generally a lot -- and the treadeoff is that generally 64-bit apps use more memory since addresses (a substantial part of data and code for most apps) are twice as large. On most 64-bit computers iTunes usally isn't hogging the CPU enough that you'd fret about the performance increases.
I'm just suprised by the excitement people have for this since in the short term 64-bit cocoa iTunes isn't going to do much for you that 32-bit carbon iTunes didn't. The real benefits will come over time because Apple should be able to spend less time maintaining it.
There is actually a TON of benefit. My machine uses around 12 gigs of ram just on common tasks, it has 24 gigs. Non used resources is wasted resources and Mac OS scales its usage of resources intelligently. Also for those of us with large libraries this is a definite benefit.