A fifth color is an ink added to a printed piece in addition to the standard cyan, magenta, yellow and black of four-color process, usually a Pantone spot color or custom ink. It requires an extra run through a four-color press, which adds cost. Some presses have five units to handle fifth colors or clear coatings.
It usually means an extra press unit or an extra pass, which can add cost.
Related: Spot Color Pantone CMYK