I think if you filled object with a opacity 1-2% black and then an equal opacity white it would desaturate it slightly, sort of janky way but maybe a faster workaround.
It's been a few years since the last forum post. I'm new to using zbrush...does the new version have anything in it now that allows you to quickly change hue, or the saturation of the polypaint like you can in photoshop? I'm asking because im trying to cut down on the step of having to take a texture map into photoshop and adjust if i can stay in zbrush.
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edit: yeah if your high poly is UV'd then what JohnnyRaptor said would work.
good point