Not a massive fan of much Country & Western but can recommend the following.
Townes Van Zandt- Just a fantastic songwriter. Heard him called a country Leonard Cohen before (not sure if that would put anyone off). The Texas Troubadour box set is pretty cheap and contains all his best stuff (first 7 albums).
Think someone else mentioned Lee Hazlewood. He is a total one off and recommend Cowboy In Sweden and Requiem For an Almost Lady (the latter is the best break up album ever!)
Here's No Train To Stockholm from Cowboy In Sweden inspired by moving his family to Sweden to stop his son being drafted.