I've got phpMyAdmin setup, but when I logout or try to browse a table I get 404 error. Everything is CHMOD as 755. Ideas? I'm also running off of LiteSpeed

Don't you miss some files? Don't you have any global rewrites that could affect PMA's scripts?

I'm using the same config file I had on a previous host and worked fine. It's a fresh upload(in binary mode), and some of the features work, and others don't like clicking the tabs or like editing privileges(I can for some of the older users, but get a 404 on some of the newer ones).

Didn't you change the mysql version to a newer one? If you did you should have executed the script to update the user data as the format of user data storage was changed in 5.0.