I'm quite experienced sysadmin, but only for a short time I maintain servers with Fedora Core onboard. Thus I've got some questions.
yes. severe lack of interested volunteers to take it up but meanwhile
Here are, I think, the most important areas:
/etc of course.
/etc/sysconfig The main place that the files in /etc/init.d look for configuration info. These files are typically sourced in the init.d file during its run. One mostly set variables there.
It's also a good idea to get familiar with chkconfig. There is some GUI version of this, but, well, you know, CLI rules for power users. :-)