If you really want to you can level your classes through pvp. It'll take a while but it's possible. Unless you mean open world pvp then no.
Additionally this won't solve your issue. Your main story quest progress will still limit you in what you can do. So there is no getting around doing that. Except buying a story skip potion but that will only get you to skip up until Endwalker. You'd then still need to manually finish all the Endwalker main story quests.

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