I'm always excited to see people getting introduced to Bujold, and I think the World of the Five Gods series is a great starting point. FWIW, I regularly re-read the Vorkosigan books from Memory onward, especially Komarr, A Civil Campaign, and Captain Vorpatril's Alliance, but rarely revisit the earlier parts of the series. Which I think just shows I'm more into space mystery, space comedy of manners, and space romantic romp than space opera.
I'm unusual in that I love the Sharing Knife series as much or more as anything else she's written--something about it just pushes everyone of my readerly buttons in all the right places.