I like to think of dew point as when the air acts, and relative humidity as how the air feels. If I am using spray paint here in Texas, I have found using the dew point is a far better predictor of success than relative humidity. If the dew point is below 60º, I'm fine (other conditions pending of course), but much above that and I'm likely to have moisture condense out of the air into the paint stream as I spray, or something to that effect.
Likewise, if it's 80º and 40% RH, it's a good day to work in the yard. But if it's 80º and 90% RH, not so much. It's also a way to help judge what a new destination will feel like - looking at the RH helps me figure out what it's going to feel like when I'm there and how to plan to dress.
At least that how I think of it.
Tony