I don't know how much time you have in Naples, but ships are usually there all day and you should have plenty of time to do both. We took a hydrofoil to Capri as soon as we docked; spent a few hours, then took another hydrofoil to Sorrento, had lunch, shopped, then took a bus to Pompeii.
If you do only have maybe half a day, either is great. Capri is beautiful and picturesque; Pompeii is facinating from a historical standpoint.
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