It can't conduct heat to human skin. The concept, in this case, wouldn't be to merely prevent a material from catching fire, but to keep the person from being burned or steam-boiled.
However, the general concept could also be applied to protecting things besides people, such as vehicles or buildings.
I don't actually know very much about the wavelengths used by DEW, so I'm not clear if water, alone, is a practical as shielding, but could be used as a heat sink, especially when factoring in latent heat of vaporization.