yes and yes to both your questions.
Once your pve character has made it to one of the areas where a pvp arena is attached (Ascalon, Yaks, Lions Arch, Dragons Lair, Droknars), they may enter the corresponding arena. To do GvG, obviously you must be in a guild and have a hall, beyond that, no problems. The only advantage to using a pvp character over pve, is that should your build not work in pvp, you can simply delete it and make it again with rearranged attributes, you don't necessarily want to do this with a pve character, and refund points can become low very fast and while a few arena fights will give you the necessary xp for a point or two, 24 (1500xp) still takes a while to earn back.
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