I think I've already commented a bit about this somewhere before, but... i have also been wondering how it is supposed to be used, as every document, or comment here, has so far just referred to different generic explanations based on the term "guarding", but which actually does not apply in this DE-5000, or the referred document has been just as vague as everything else.
On DE-5000 the way the guarding is wired inside the device, it won't reduce leakage the way the guarding is often (or usually?) understood (i.e. to track the measurement signal so that the measurement signal to guard voltage difference is zero, so no leakage is possible for the measurement signal). Alas, the "guard" in DE-5000 is simply connected to the negative supply plane on the device, and the measurement levels have a bit of positive offset, so there will be (a little bit of) leakage.
I would imagine the idea would be to connect the guard to target device's ground/negative plane (assuming the component/circuit is still in the device), so it will make the DE-5000's negative supply level to track whatever the guard is connected to, so it might reduce noises indirectly. Note, with the usual way the clips/etc are wired, there won't be full end-to-end connection in the shielding, even with guard connected, so it probably won't help against noise the way e.g. how oscilloscope probes' shielding/ground clip works. Note also that if the DE-5000 is powered from the DC input (not with battery), connecting the "guard" = DE-5000 negative supply = DC brick's negative supply might have some less useful effects, too.