Piccolo learning the technique in 6 days would be absurd, regardless of the massive gains that he made in that span. Kaioken is not a technique one can just pick up with ease. Given the fact that Piccolo's BP increased so much during the 6 days, it's clear that was his focus - not learning the Kaioken technique.
The humans not learning it is questionable given they had over a year to learn it, but Gog's explanation probably works best. Plus it's arguable that Tenshinhan incorporated part of the technique into his Shin Kikoho.