Science Fiction and Fantasy really fall on two opposite ends of a spectrum. In some ways you can think of the individual books falling somewhere between the two sides. Stories like 2001, Rama, Ringworld, and such will fall closer to the "Science Fiction" side of the spectrum while Dragonlance, Lord of the Rings, and other High Fantasy stories fall closer to the Fantasy side. Those are all easily distinguishable. Stuff like the Pern series tends to hover to either side of the middle of the line. A book like Enemy Mine, while clearly sci-fi, isn't focused on technology and actually takes efforts to abandon technology altogether for a significant portion of the story. This might fall a little closer to the middle.
When managing my book catalog, I have no issues labeling a book as Science Fiction AND Fantasy if I can't decide either way.
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