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Notes -
The original "Foundation" trilogy is the place I'd start, if you're okay with the old-sci-fi "Sense of Wonder, Big Ideas, What's Characterization?" style. For the first whole book the plot jumps from generation to generation fast enough that when he does give you a fascinating character you have to resign yourself to soon saying goodbye and at best hearing about that character again later as a historical figure.
"The Caves of Steel" (followed by "The Naked Sun", "The Robots of Dawn", and "Robots and Empire") would be option B. Sci-fi/mystery crossovers, maybe not as good overall but not nearly as weak on character development.
There's a two-book prequel series to the Foundation trilogy, which was my favorite of all the fiction he's written, but which I wouldn't recommend reading until after the above 7 books.
I think that covers all the strong recommendations for novels.
His collaborations with Robert Silverberg were good, but they were all just fleshing out earlier novellas, and honestly you could just read the novellas instead to get 90% of the quality in 30% of the time.
He got started with short stories, and some of his best stuff is in them, but any particular anthology is a mix of quality, except that his last couple ("Gold" and "Magic") I found disappointing.
His "Empire" novels ("The Currents of Space", "The Stars, Like Dust", and "Pebble in the Sky"), weren't best-of-the-century things like the Foundation trilogy was, but I did like them better than The End of Eternity.
He had a couple kids' book series. I remember loving "Lucky Starr" and being disappointed by "Norby", but I read "Lucky Starr" in elementary school and I wouldn't dare guess how it would hold up to an adult. Perhaps Norby was just as good but I found it in middle school or high school and had aged out of the intended audience.
Edit: I almost forgot to mention "The Gods Themselves" - I wouldn't even put it above the "strong recommendations" line myself, but in some ways it was one of the most unique and interesting books of his I've read, and I've known other people to say it was his best, and it's perhaps a safer recommendation (stand-alone work, not "you should read these other seven books first!") than my own favorite.
I was always one of those guys who loved his non-fiction much more than his Sci-Fi. Asimov always stayed true to the reputation people often pinned to him as “the greatest explainer of the age,” and he was truly remarkable when it came to that. When I read the Foundation trilogy though, it just kept coming through to me, over and over and over and over and over again just how sterile his writing seemed to feel; and it wasn’t at all to my liking.
IMHO the Foundation trilogy gets much more humanized halfway through, and even for the first half "sterile" is an overstatement, but you're at least directionally correct, I must admit.
I'd agree his non-fiction was better than his fiction, it's just harder to recommend because there's so much to choose from! Hundreds of books instead of dozens, in so many fields that it's hard to say that a fan of one subject would equally appreciate the others. "Asimov's Guide to the Bible" was perhaps the most in-depth example I can think of to recommend, but by far my favorites were (the anthologies of) his pop-science essays.
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Thanks, I'll add some of these to the list.
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I vaguely recall enjoying the Norby books, though I remember almost nothing about them except the weird telepathy punctuation (was it italics with guillemets?).
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