I'd be more than happy to help. I currently work as a software dev for an options trading company. Most of my work is PHP and MySQL based, but I'm pretty flexible as far as platforms go. I'll also pass the word around to my co-workers, maybe one or two will also be interested. Just pulled up the programming and developers guides and I'll be going over them now. Let me know what you need me to get started on.
Jimmy, welcome! We'd definitely love to have you and your friends help us out. PHP skills are definitely needed when trying to work on the Web Admin and of course MySQL skills are great. DCE, and its devices are written mostly in portable ANSI STL C++, referencing constants, and data inside the database, code and data are tightly coupled.
You can also write DCE devices in Ruby using the Generic Serial Device (GSD), which is a wonderful way to write small simple device controls very quickly.
We also use shell scripting, perl, and awk for underlying system script integration and for synchronization between some parts of the subsystem (i.e. between our Asterisk DCE device, the Telecom Plugin, and Asterisk).
Feel free to drop by the #linuxmce-devel channel on freenode to chat with us.