As FFF says, Chandler Air Service are the best place in the valley. They do like to get to know you though before they fully relax, which is not a bad thing, but it's a bit strange at first. Their instruction is the best around for a flight school, they will give you a hard time
Another choice would be Falcon Executive Aviation at Falcon Field, they cost a bit more. Falcon Exec have a superb reputation for maintanance and people bring their planes in from all over the Southwest, and I think that puts the prices up for the rental fleet. Their owner is one of the most honest and decent people you will find in business.
Plenty of places to see and do. Fly into McCarran in Vegas at night and mix it with the big boys.