'Van Lear Rose' The recent Loretta Lynn LP with Jack White is very good, if a little abrasive, stylistically.
Would agree with many of the recs already made.
Charlie Rich's Sun Sessions is also excellent. Now out of print, this is available as a torrent from various places. Country with some jazz, blues and R & B stylings. 'Closed for Repair' is one of my favourite country tunes.
From the very early days of this kind of music, you may also like to check out Mississippi John Hurt. Considered a country blues player by those that like to put labels on music, he has a mellifluous style that was obviously an influence on later country artists. An amazing guitar player, he melded country blues, ragtime and elements of popular song of the time (late 20's) and had a beautful voice. I have
this and it's great.
Also, a little off the country path, but utterly wonderful is western swing, of which the greatest practitioner was Bob Wills. Western Swing is often considered to be one of the natural pre-cursors to white Rock n' Roll, melding pop, country and blues with Jazz & bluegrass virtuosity. More barndance than Lonesome Me, this style was popular from '35 - '48 or so. I'd reccommend the Bob Wills Tiffany transcriptions, as these radio workouts stretch out beyond the confines of a 78 side. AFAIK, there are 9 volumes of these and they're all great, but out of print, so I'd reccommend whichever you can get cheapest from your retailer of choice (just search for "Tiffany Transcriptions"). IMHO, vol 6 'Sally Goodin' is the best.
edit: Bob Wills on You Tube
here
Simon