I have lived in Murrieta for five years, and living in Temecula for about two years before that.
Here is my list:
Temecula has had better city government, smarter people and less rancor.
Temecula is 2-3 degrees cooler.
Both Murrieta and Temecula have some great schools. Temecula is laying off some teachers and closing some elementary schools, while Murrieta currently plans no layoffs and has a new high school going up.
Murrieta does seem more conservative: less upscale retiree types.
Temecula has stronger retail: the mall redo is great and Old Town is an attraction.
Murrieta is Forbes Magazines no. 1 “Subprime Boomtown.” Lots of repos and price drops here early when the bubble burst, but lots of new buyers at the moment. There are some great home values, especially if you want a large home and/or large lot.
Murrieta has the Santa Rosa plateau, which is stunning.
Honestly, the two are similar enough that I think of them as one town called Murriecula.