-Runlevels are each different RH by default
-Config files are different (though mostly still buried in /etc)
-Tools are different (things like bringing up the network or restarting services)
The basics are the same. But you're going to struggle finding what you need. I'm no expert (just use RHEL sparingly at work when necessary). I think it was harder to go from Debian to Red Hat than it was for me to go from Windows to Debian. At least things were completely different between Win and Debian. In linux to linux moves I struggle because my brain works in Debian and everything is similar but slightly different. It's like being forced to eat left handed. I won't starve, but it's not pretty.
I'd pore through some of the manuals on the Red Hat
site. You may need to go back and look at the RHEL 4X manuals to get the "Intro to" type articles.