As a venue...ease of getting in and out, sound quality, and sightlines I'd argue Starlight is better (been to RR 11 or so times so I'm very familiar). Now, which is the more unique venue and one you should probably go to if you are picking just ONE venue to see a show at? Then you go Red Rocks. Once you've been multiple times the mystique wears off and the time commitment (often 7-9 hours committed to getting there from Denver, parking, walking up, waiting in line, seeing the show, then getting home) becomes an irritant. Saw 3 shows in a week one year and that pain grew old. Red Rocks also has the best concert calendar of any venue in the country, one of Starlight's weak spots (too many wasted dates).
Oddly enough I think White might be the worst sounding show I've see at Starlight. His vocals weren't loud enough, bass was muddled, and the overall volume felt 60-70% of what it normally is. Being that I've seen about 30 shows there, and about 4 this year, I think it had to have been his sound guys that were to blame. Show was still great but they really missed the mark.