What a Way to Go! (1964)
I Moxied this and finally got to see it last night. Since it won't be on anytime soon (that I know of), you're going to have to rent it!
The star power alone is reason to watch: Shirley MacLaine, Paul Newman, Robert Mitchum, Dean Martin, Gene Kelly, Dick Van Dyke...
MacLaine plays Louisa, a woman who wants the simple life: a little cottage in the country, true love, and maybe a couple kids. She only seeks men with meager lifestyles, but no matter what she does, she ends up with men with too much ambition and motivation!
Thinking she's cursed, she tries to get rid of the bad luck by giving a check to the IRS for all her millions. Instead of accepting it, they believe she's crazy and send her to a shrink, where we hear about her life as a black widow amongst unfortunate -- yet fortunate -- men.