I'd agree with the sentiments of those who say "buy anything". Each Womack lp contains moments of soul history.
The Poet lps are probably the most accessible, but probably the most uniform and least individualistic examples of his work. My favourites are "Communication", "Understanding", "Looking For A Love Again", "Facts Of Life" and "Home Is Where The Heart Is", which all contain the essence of Womack at his most dazzlingly creative: stretched out, completely spontaneous examples of a supreme soul artist connecting with his audience in a way which is still breathtaking.
These albums also contain plenty of covers of pop hits and idiosyncracies such as the ode to Hillbilly moonshine making "Copper Kettle" which to the uninitiated may sound a bit strange, but which to me are quintissential Womack: I love his version of Bacharach & David's "Close To You", for example, which comprises about eight minutes of the most natural, intimate and confidential example of an artist talking on a record.
The Poet series and the MCA albums after these sound a bit more corporate and polished: they are very much products of LA as opposed to the funky and loose arrangements of the Memphis and Muscle Shoals work of the 70s heyday, but all contain some stunning songs.
Even the largely unappealling "Last Soul Man" set (which has a truly horrible version of Living In A Box) contains the stunning "Gina" a crushingly soulful tribute to his (presumably long suffering) wife.
Agree with JOT on the Valentinos retropsective. It's interesting to me that the best two tracks are the ones which feature Bobby on lead vocals as opposed to his various brothers: "See Me Through" and a magnificent demo of Wilson Pickett's "I've Come A Long Way", both of which were unissued at the time.