This isn't a popular airline around here but flying Southwest Airlines out of Love may be a great alternative if you want to rack up lots of free tickets for family vacations in the USA. SWA has great schedules to most cities in Texas and Florida. If her regular territory will be short haul flights (neighboring states) it will take a long time to rack up free tickets on American Airlines. You will only earn 500 miles (without any elite bonus miles, once and if she makes elite status) for most short haul destinations. It takes 20,000 - 25,000 for a free domestic roundtrip ticket on AA.

SWA works on a credit system. You earn one credit per segment flown and you can earn double credit if you book your flights online. It takes 16 credits to earn a free trip. So if you booked online earning double credit for every 4 round trips you flew you would earn a free domestic ticket anywhere SWA flies. This is great if you have a big family.

AA should probably be your international carrier since your wife will be making a few international flights.

Hotels all depend on where her company has negotiated rates and if they have spending limits in certain cities. Hilton has a bigger variety of brands while in general I think Starwood has nicer hotels.