Rooks and bishops follow the obvious geometry of the square chessboard. Knights are the natural complement of rooks and bishops: they move to any of the closest squares neither a rook nor a bishop could reach.
Pawns defend each other and form the game's "structure".
Queens are rather arbitrary (you could have rook+knight or bishop+knight instead of rook+bishop), but a strong piece is needed to allow for dynamic play.
On an hexagon they don't really make sense. Is there a more "natural" set of pieces that's built on the geometry of an hexagon rather than being an awkward translation of the usual chess pieces?