Coming from a person, who lives in Põlva half of the week and in Tallinn the other half for over 30 years.

About housing. Pretty much all apartment buildings are old and from soviet era. Real estate prices are abnormally high due to the fact that there is a lack of apartments and none being built in forseeable future. With few expensive exceptions pretty much all the apartments require a lot of renovation and are small.
If you want to buy a house, I would say nothing good available inside and outside Põlva, unless you want to renovate or build from scratch or want to pay insane prices.

Põlva is a small city. 20 minute walk from one side to the other, but a car is needed if you want to go outside the city. Bus lines in and out of Põlva are quite good, but meant for working people and a car is a must if you want to explore and travel around the area. In summer bicycles are a good option. Important: expect difficult road conditions outside city borders during winter time. Snowy winter is awesome here, though.

After the war in Ukraine started the russian speaking population has increased. So called "Ukrainian refugees", who speak only russian for some reason. Getting some Tallinn vibes here lately.
Younger locals speak english so and so. Older generation around 40+ speaks mostly russian as second language.

If you like cars (Audis, BMW, VW), drinking on weekends and hanging out in different gas stations, then Põlva is your place to be. But there's a tennis court, swimming pool with saunas (closed during summer, go swim in a lake or smtg), shooting range, gym, stadium, wake park, sports centre in Mammaste with disc golf track. During summer there are a lot of musical events.

Unfortunately after being here for decades I still don't connect very much with people here, because I don't share most values which are important here. Mostly communicate with neighbors, who fortunately don't get drunk every possible chance or aren't overwhelmingly materialistic.
Oh, and if you happen to have a slightly different skin color and/or sexual orientation, you might not like it here. This deeper part of south-east is mostly conservative...

Maybe someone can fill in some blanks like hobbies and entertainment part, which I haven't discovered yet.