Pompeii is 240 km south of Rome, about 35 minutes by Circumvesuviana train from Naples Centrale. The site is enormous: 66 hectares of excavated Roman city, about 2 hours from Rome by the time you account for the metro connection to Naples and the Circumvesuviana. Tours handle all transport and include a guide, which matters because the site without context is overwhelming.
DIY is cheaper and more flexible. The train route is: Rome Termini → Naples Centrale (1 hour, high-speed), then Circumvesuviana train from Naples to Pompeii Scavi (35 minutes). The site entrance is a 5-minute walk from the Pompeii Scavi station. A guide is strongly recommended, the site is too large to understand without one. You can buy a guide at the entrance or book one through the tour. Browse tours →
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Pompeii is not a museum. It's a frozen city. The Forum, the baths, the houses with their frescoes still intact, the street of bars, all of it preserved under the volcanic ash that buried it in 79 AD. The plaster casts of the people who died are the most emotionally affecting thing, positioned where they fell, curled in foetal positions. They're on display near the Marina gate.
Sources: Parco Archeologico di Pompei, official site · Wikipedia, Pompeii · UNESCO, Pompeii.