What Master1a said is pretty much spot on. Let me add that the online multiplayer PvP action is only available on the Diplomacy expansion. (You might be able to find some games on Original Sins and the Entrenchment expansion, but almost all of the action is on Diplomacy.) Sadly, you often will have to wait to play a game but there are still a couple 4v4 and 5v5s every day. As a general rule, it's better on Fridays, Saturdays, and Sundays.
It's a great game, btw. It really deserves to have 2000+ people online at any given time. It had some technical problems early on, and it seemed to appeal primarily to the single player 4x crowd and not the online multiplayer RTS crowd. Another reason for the low player counts might be the length of time needed to play a game. Your average 4v4 or 5v5 lasts about one-and-a-half hours.
Hopefully the upcoming "stand-alone" Rebellion expansion will get the game on store shelves and into the front of gamers' minds again and Sins online multiplayer will be reinvigorated with a large infusion of fresh blood.