Not sure how much I can help but I'll share my experiences. I run a three bulb set up and have yet to be 100% satisfied with bulb combos I've tried. My current setup is my favorite so far. It is the first time I've run two blues and one white and is set up front to back as follows; ATI Blue+, AquaScience Special 15K, ATI Blue+. The overall look is blueish, which = vibrant colors but still supplies good PAR. When the time comes to replace the AquaScience bulb I'll either go with either an ATI aquablue special or a GE 6500K. ATI if I want more blue or GE if I decide on less blue.
As far as what to use to highlight different colors... All I can say is ATI blue+ kick the cr*p out of CurrentUSA blues. I haven't tried any of the "purple" or deep red (ATI pro color) bulbs so I can't comment on those.