For Bujold's Vorkosigan series, I think A Warrior's Apprentice is the best starting point for someone new to the series. It gets you into the story fast, doesn't require knowledge of the earlier history, is great fun and great character building, and if you like it, then you can march straight forward from there and pick up the backstory when you feel like it.
And by the way, most of the Vorkosigan books are available in omnibus collections in ebook from Baen. Ridiculously low priced, or at least they were when I bought them.
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