Here's what I know:
(I do not/have never worked for them--but I am a lifelong resident of the Land of Enchantment--so I have more than a casual interest in Grande)
They pay decent. One of thier pilots said somewhere in the $30K range. I don't know if that was for someone new, or someone who had been there a while.
The company seems really cool. I've met the owner a few times and he's a real nice, honest guy (not that we talked about airplanes though--he didn't know I was a pilot). I've also never heard a Rio Grande employee complaining about anything the company does. And I've sure tried to get some dirt out of them.
I beleive all the pilots are based in Albuquerque. They might have one or two that live in Taos as I think they have an airplane spend the night there.
I don't think they are hiring now. Last time I knew they were (well over a year ago) they wanted a good deal of time to fly the Caravan--3500TT if my memory serves.
Personally, I'd love to work for Rio Grande Air, but the requirements are much to steep for me anytime in the near future. But it seems like a great company, and rumor has it they were thinking of adding King Airs to the fleet.
Hope that helps. I'm just a bystander, but a local one.
Dan