Not all game support multi GPU's, that being said both are on all the time. To see for sure if the game is utilizing both:
1.) right click the Ati icon in your taskbar
2.) Hover over the first GPU, the menu will come up
3.)At the very bottom of the list it will say CrossfireX settings, under that menu select show Ati Crossfire logo
Once you have done this, the Ati logo will show up the in the top right corner of the game you are playing reassuring that it is using both GPU's. If there is every an instance when you need to turn off one of the GPU's follow these steps:
1.) Open Catalyst Control Center and Select under the 3d option Catalyst AI
2.) Just check the Diasable Catalyst AI and now the second GPU will be disabled.
Hope this helps. And Btw even when it is using both for some reason most game will say 1gb because I think it is only looking at what is allowed with one GPU.