What happens if you place the PrintTable before the first if statement? Does it show everyone there too?
I'm guessing you have other code that's inserted all your players into inPvP, or would be erroring different (see below).
Also
table.KeyFromValue(inPvP,calling_ply)!=calling_ply:EntIndex(I'm pretty sure that's not going to evaluate the way you expect, and think it could very well be true most of the time.
Due to
table.insert(inPvP,calling_ply:EntIndex(),calling_ply)line, that simply inserts into the spot in the array, it doesn't necessarily make that new insertion entindex the key.
And, if it's out of bounds, will likely give you an error.
Say you have one player in inPVP, if you try to insert in position 4 because the calling_player's EntIndex is four, Lua doesn't like that.
Here's rough example lua code from Tutorial's point -
http://tpcg.io/TgtzuV (when loaded, click "execute" and watch output error "out of bounds")
(I don't have account there, so not sure how long that link exists)
It fails. table.insert tries to insert at position 4 and fails for my table with only 2 in it, so I think your table is already large enough not to error.
Something else is likely adding everyone, not this code.