1. If you are moving to a different computer,
and you have any DRM-protected downloaded/purchased files, you should first Deauthorize the old computer (
Store > Deauthorize This Computer) and then Authorize the new computer (
Store >Authorize This Computer) after copying files and configuring iTunes on the new computer.
2. All of the iTunes database files (
iTunes Library.itl, iTunes Music Library.xml, iTunes Library Extras.itdb and iTunes Library Genius.itdb) are not stored in your Media Folder location, but instead are stored on your primary drive under your profile in
/Users/username/Music/iTunes. These files contain all the playlist, play count and other customization data. There is also an Artwork folder that contains all album cover artwork that is not contained in the song files, so you want to copy
all files and folders from that location to the same internal hard drive location on the new computer.
3. Your external media drive on the new computer should be configured with the same drive letter as your old computer if possible.
The problem many have run into is that if the external media drive is disconnected, when iTunes is started and doesn't see the drive, it will change the iTunes Media Folder location to default to the internal hard drive location under your profile. So check under Edit > Preferences > Advanced tab that the media folder location is correct and pointing to the external drive.
Here is a thread that was recently resurrected that you can read through
http://www.audiocircle.com/index.php?topic=66286.0 and I'm sure there are other threads here on AudioCircle, as well as much information available on the Internet when searching for "iTunes Library". But if you follow the above guidelines you should have a smooth transition.
Steve