OK, here are a few programs I would recommend you get:
Mumble – http://mumble.sourceforge.net/ – Voice chat software, a much better option than using ingame voice communication.
Teamspeak – http://www.teamspeak.co.uk/ – Same as above, some people prefer TS, some people prefer Mumble.
Ventrilo – http://www.ventrilo.com/ – Another VOIP option.
mIRC – http://www.mirc.com/ – Internet Chat Relay, a good tool for finding pcw’s on #5on5 or whatever channel it is these days.
Are good IRC channels for finding matches.
There is likely a wealth of information around the internet about setting up and using these programs, so I won’t waste my time explaining how. Google is your friend.