The big thing to remember here is that you can direct iTunes to the location of the library. This can be done in the shared folder on your Mac for multiple users on that computer. And now we have the PC in the mix and you could share the library on the network for each computer to use or copy the library onto the Express from the computer that has the most free space available and make it a shared item.
Just do one thing from the beginning, have all the songs on one computer in the beginning and perform a backup to disc (use DVDs) once all the importing has been done from CDs, DVDs, etc... Then when there is another significant addition to the collection do another backup on that same machine and these discs will contain the updates since the last one.
What does this do? If your hard drive was beamed aboard an alien ship that left with your music library, after installing another drive and setting up your account, Apple ID, etc... you open iTunes and insert disc #1 and iTunes will know that this is a back set and begin returning the music, playlists, etc... back to the last backup point.
So setup the entire library and backup (easiest on the Mac and probably has a DVD burner if newer) and then figure out how you want to share. If you still have access to AppleCare, call them before the support ends on the last Mac product you bought and have them walk you through sharing the library from the Express and the best way to update the share library if that is how your going to go.
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