I currently have PPRO 2.0 and am considering Cineform as my intermediate. Will Cineform work well with this card and will Cineform allow me to use the DVI port to display the overlay on an external LCD?

We work with all cards that can redirect their overlay surface to an external monitor. So yes you card is very likely to support this. If you can get Mediaplayer to output to your second monitor, then CineForm tools will work.