Personally, I would roll a 2nd team for PvE, and have the shamans stick to PvP. I have a paladin tank, holy priest, frost mage, afflic warlock, and elemental shaman as a separate PvE team. They breezed through instances until I got bored of instance running.
Will 4 shamans and a paladin work? I don't see why not. If you want a paladin on your pvp team, it's probably better to recruit someone else to play the pally, and you control the shamans.
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