All of the early Palace/Will Oldham stuff is great on the post-punk side of things. I'm also a big fan of the Violent Femmes second album Hallowed Ground, which is very country influenced (obviously most especially "Country Death Song") and considerably darker than anything else they did. Of course the first three or so Meat Puppets records are classic cow punk too.
I love old Dolly Parton songs (nothing after the '70s of course.)
Kenny Rogers first band Kenny Rogers and the New Edition were actually an awesome country psych rock band. Suprisingly heavy stuff.
Bob Wills and the Texas Playboys are great country swing from far enough back that it doesn't suck.
Ray Charles did some incredible blues/soul crossover stuff in the '60s.
Chet Atkins is deservedly considered one of the best guitarists in any genre.
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