It's a little confusing because the "Multiplayer" button is for LAN games. The real Multiplayer button is "Ironclad Online". So, click the Ironclad Online (ICO) button and register and ICO account and a player name. You'll then login and go to the Lobby. To see available games click "Join Games".
Note that your best bet for finding games is during European and North American prime time, between 3 pm U.S. EST and Midnight U.S. EST. Also, weekends are better.
Welcome to the online multiplayer community. (Just make sure you've played it for a couple weeks in single player first and have a good understanding of all the races and their strengths and weaknesses because the human competition will be tougher than anything you've ever experienced in the single player game.)