Yes - whatever position you set in the Photoshop file will be the default. So make that as crosseyed and goofy as possible and you should be set. You may run into some sync/update issues if you're doing any additional rigging in the puppet panel inside CH - so try importing a fresh psd with crossed eyes and see how that goes.
Make sure you're also clicking "set rest pose" to calibrate your character (the eyes can get off base if you don't). And with your character selected in the scene timeline, try adjusting the Face > Head Scale and Eye Gaze properties on the right to lower numbers for less dynamic movement. And if you want to get real crazy, you can record a pass with only the "Eye Gaze via Mouse Input" armed, which will let you control the eyes completely with the mouse.
One more tip: there's a hidden feature where the eyes can move independently. You can toggle this on/off by hitting "E" when the Camera & Mic panel is focused. This will be removed in Preview 3, so it's not accidentally enabled.
ahhhhhaa ^_^ that's what i'm talking about