I'm not sure if this is going to help or muddy the waters more.
First, I've seen photos of Charo pieing herself with "Shakespeare" looking on. I don't know what show that was from, but it would be the same era as the Captain and Tenille show.
Second, the Hudson Brothers had a show, with their name in the title I think, that ran in what was then called "prime time access" in the mid 70s. The idea was for the networks to give the local stations half an hour back, for the stations to use for "local" programming. What ended up happening was that Monday-Saturday, most stations scheduled syndicated programming: old sitcoms, game shows and some syndicated shows made specially for that half hour of "local" programming.
Sundays, for awhile, the half-hour given back was 10:30-11:00 p.m. And today, that half hour is filled with syndicated game shows or entertainment news shows. So much for "local" programming.
At any rate, one syndicated show I watched in that half hour was "Madhouse Brigade." Among its skits was an English Leather cologne ad spoof where the actress would say "My man wears EL or nothing at all" and then there'd be a reaction - maybe the man in a domination outfit or, in one version, she was pied well (but little reaction shot).
Another show was the Hudson Brothers. The guest star was often pied. Florence Henderson was pied; that's where those pied photos of her come from. My favorite was Karen Valentine, who was still very cute despite dying her hair blonde. She was pied to "Chattanooga Choo-Choo" -- but the pie thrower MISSED on the first shot, and she laughed. The other hits, in the time to the music, were very good.
At any rate, MK, what you're looking for is the syndication series by the Hudson Brothers, with their name in the title somehow.