Hey there. Just attended a reunion at Whitman. Walla Walla is a lot more urbane than when I went to school about 15 years ago(!), because the wine industry (then nascent) has really taken off.
Walla Walla isn't a big town, but Whitman brings in a pretty constant stream of cultural offerings (politicos, concerts, performances, inspirational speakers, authors) to meet that gap (a lot of students come from Portland, Seattle, and Boise). The local/organic food movement has got a foothold now, wine is Very Big (and probably will be forever), the Walla Walla Symphony is often touted as the oldest west of the Mississippi ... . For a quiet night away from home, there are now five ZILLION bed and breakfasts catering from "I love to live with antiques in the middle of town" to "I want a minimalist space with a yoga focus in the fields 12 miles outside of town." (That latter apparently hosts groups from Walla Walla on retreat fairly regularly.)
The colleges do a lot of theatre and there are a couple of dance troupes in town; a Renaissance re-creation group based in TriCities comes down to Whitman every year in April for Ren Faire (and last I checked the Society for Creative Anachronism had a decent chapter in Walla Walla itself).
There are mountains and rivers within easy car distance; I suppose the old bike rides through the wheat-country have transformed to bike rides through the wine-country ;). Lake Coeur d'Aliene(?sp) is a popular getaway spot as well.
More pop-entertainment-y: The nearest major indoor concert venue is I think in Tri Cities. (Outdoor venue George in the Gorge, as mentioned below.) The bar scene is still pretty ... rustic/divey (from what I heard ... I didn't even try this during the reunion ;) ). When I was in college the nearest nightclubs were in TriCities and there was the Cowboy Club and immediately next door the popular/alternative music club (name unremembered), and that was IT. One or two of the bars in Walla Walla have dancing, but they are kind of bars first and dancing second.
Walla Walla has a tiny commercial airport but decent daily connections to major NW cities for transfers, no train station (but trains roll through town, so if that is a noise problem tell your realtor), and I think may have fallen off the Greyhound Bus stop-list finally.
Mall-type clothes shopping at the Bon (equivalent: Macy's) on Main Street or out at the west end of town at Blue Mountain Mall. Major grocery about every 2 miles (Albertsons, Safeway, Super1). It's still very much a farming community, so good hardware stores ;).
The central parts of town have great early 1900s houses (if you can stand the upgrades necessary to insulate etc.); pretty much as you move out from the center you find newer and newer houses. Be aware that the closer you are to one of the colleges, the more likely you will be living next to house commonly rented to students, with all that that entails noise/behavior wise. When I went to college back in the 90s, I had a conversation with a man who lived "on the wrong side of the tracks" (near the Penitentiary) and he said people living near the Pen always left their car doors unlocked because when cons broke out of the Pen they would steal cars for the first leg of the getaway and leave them someplace, and if your car was locked they'd bust in and you'd have damage but if your car wasn't you'd get it back from the police in a day or two in OK shape ... I don't know if this was true, but I sure didn't look into renting near the pen while I was in college!!!
Politics: generally conservative, but in the don't-stick-your-nose-in-my-business kind of way (the college is generally liberal). A series of efforts in the 1990s to bring awareness to gay issues took root and I wouldn't say there is no ill feeling toward homosexuality but in general the nasty active type doesn't show up and most people I think are at least don't ask don't tell if not actually OK with it. The nicest bar in town has a very public gay night, last I heard (a few years ago, it was in a college newsletter I think).
What might throw you the most is something NWers often forget: there are nearly no people of color in Walla Walla, and nearly all the ones there are are associated with the college, still. I've never heard trouble from "the townies" about this, but I know my friends did used to get some stares, especially if a clearly bi-racial couple was out in town. Washington and Oregon have a pretty negative history in race relations.
Dust storms: MUCH MITIGATED, but they do still occur. Big education campaigns were instituted in the late 80s(?) to try to convince the farmers to keep cover crops etc and prevent their top soil blowing away. Walla Walla is a pretty dusty place, though, even without noticeable storms.
As for realtors, check the Chamber of Commerce site and click some links until you find a realtor who feels comfortable to you ... unless someone has a brilliant recommendation ;).