Assigning applications to multiple desktops (Spaces) across multiple monitors
I know that the 3rd party application TotalSpaces2 has the ability to assign program's to specific spaces of Mission Control. Also, I know that you can use separate spaces for separate monitors in Mission Control.

So, check out the trial of TotalSpaces2 (for Mavericks) or TotalSpaces (for Mountain Lion) at http://totalspaces.binaryage.com/multi-monitors2

(I don't have a commercial interest in TotalSpaces2, I just started trying the program myself)