You can log into the itunes store and start using your account at any time - there isn't really any "transfer" going on, for that part.
You do need to transfer the music files and the itunes database, though. Do that the same way you are transferring over other stuff like digital photos, browser bookmarks, etc. I've used my home network in the past when we've gotten a new PC.
For itunes, the important folder is C:\....\iTunes. Just replace that folder on the new machine with the iTunes folder (and all its subfolders) from the old machine.
Have a look at the new PC's preferences to make sure they're set up correctly, and don't forget to deauthorize your old PC if you're getting rid of it. And....don't get rid of it until you are sure you have everything set up like you want!
I'm not real computer savvy so Im not sure what you mean. Can you explain? I have my music on my playlist in my account on Itunes...I dont have them saved anywhere else.
The songs, movies, and anything else you see in itunes are files that are saved on your PC's hard drive. The playlist in itunes is simply a computer program showing you a prettied-up list of all the hard drive files.
You need to get the files moved from one PC to another.