Hi Six,
As the others have posted, there are many ways to go here - good and bad.
Those listed by the others are good to me too...there's so may genres under the country name.
If you want old-school you should also try Hank Williams sr. and Patsy Cline...go well well with Merl
Blue grass calls fro Bill Monroe and Flatt & Scruggs...(and many others) The new band Nickel Creek is awesome too (I've never heard mandolin playing like that!)
Swing stuff - beside Bill Monroe (a must!) - can also include Asleep at the Wheel (and many others)
Allison Krauss & Union Station almost deserve a category unto herself/themself - awesome singer/players/band)
Also, check out Junior Browm. He invented this guitar (half steel half electric) and calls it a "guit-steel". He's an awesome player and just plain good!
I've dabbled in writing/pitching commercial country and while it is indeed a craft in the first order, in my car I rarely listen to it - opting instead for outsiders by the likes of Lyle Lovett, Lucinda Williams, Mary-Chapin Carpenter and those liek above.
Others that are CERTAINLY worthwhile more in the contemporary vein include, Vince Gill, Patty Loveless, Sons of the Desert...even the Dixie Chicks are a good listen. I'm afraid I'm out of touch with some of the really NEW acts out. There maybe some good ones that others can post here. (by and large the whole current scene - to me - sounds sooo manufactured and homoginized ...)
Album names?
I by no means have a large collection, and still have much to learn and hear, but here are records that I thoroughly enjoy:
Clint Black - "No Time To Kill"
Lyle Lovett - "Step Inside This House" and "Road to Encinada"
Allison Krauss "So Gone, So Long" (I think that's the title)
Best of Hank Williams Sr.
Lucinda Williams - "Lucinda Williams" (has Big Red Sun Blues on it) also the "Car Wheels on a Gravel Road" cd
the soundtrack to "O Brother, Where ARt Thou?" - it's an awesome collection to get your feet wet too!
Oh well, That's enough for now.
Have fun!