I started with Warrior's Apprentice and then jumped straight to A Civil Campaign because those were the two I happened to find in a charity shop. I was hooked, but hopelessly confused.

I'd resisted reading Bujold for years before that due to trying The Spirit Ring and not getting along with it, and having a dim idea that the Vorkosiverse books were Worthy Books About Disability. That'll teach me to make judgments about books without reading them. :p