As a Pueblo/Pueblo West represent, you could do either.
If I were in your shoes, I'd say you could buy or rent a nice home for that in Pueblo or Pueblo West and do great here if the food and entertainment/shopping/etc. is up to par for you.
I don't know much about Pueblo grade schools. You probably have a number of schools in the city limits of district 60 (if they do districts for k-5) and a number of schools in the district 70 county (Mesa area, Pueblo West area, or Colorado City/Rye area). Does it have to be 5th grade? Would she consider teaching at the Middle School (6th through 8th out here) level as well? Then you've got your charter schools (can't think of them now. She being a good teacher, she'd be welcome here. I don't know the exact stats to the schools in Pueblo. Like most towns, academics are a tad better in the 70 county schools than the larger 60 schools-STATISTICALLY! This doesn't mean an individual can't go and excel at the big schools, right?
Lastly. You can move up north and commute. If you're gonna do that, you might as well go up a bit into Springs and be amongst the nicest neighorhoods for the kids/ shopping/ entertainment/ food, than Fountain, but the commute would be better in the south end. I can get from P-dub (Pueblo West) to the CS airport in an hour flat-that's door to door. I think it would be a bid much to live in Briargate and drive all the way to Pueblo for work.
Good luck with this. I'm sure many in the Springs can help you from here. Take it away CS.
Add: If you're considering Pueblo, let's say you're an avid golfer. If you can afford to buy/rent near our golf courses then you might consider the Walking Stick area, Pueblo Country Club/ Ridge/ Eagleridge area, Elmwood Golf Course area/ Regency Ridge Park area/ El Camino area, or
Desert Hawk Golf Course/ Liberty Point Pueblo West/ Pueblo Reservoir area