Heck, ENT went the easy and dull route when establishing that Orions are the green guys!
Before ENT, we only knew that the green gals were "Orion slave girls". Possibly just a green species being trafficked by the Orions (who themselves were as blue as shown in TAS, or then a conglomeration of species, a crime syndicate as in DS9, or whatever), then. Or possibly women of whichever species, tattooed green as a mark of servitude.
As for the true effect of the pheromones, we know it doesn't work on Tucker, and it doesn't work on T'Pol, and T'Pol offers speculation as to why this might be. But what it does on the other folks is simple enough: it gets them drunk, after which the Orion women can tell them what to think and what to do.
We see no attraction to the Orion women unless the women actively command the men to be attracted. We see general passivity from those the Orion women fail to explicitly command.
It's way different form the tears of the Elasians, which are a direct enslaving agent with no actual aphrodisiac qualities. Kirk may be confused, but he's also enslaved to the Dohlman specifically, not vulnerable to suggestion generally.
It's way different from the Venus Drug, which merely makes the user radiate self-confidence and therefore appear more attractive. The males are attracted, the women either attracted or jealous - but this is not drug-induced behavior, it's something Kirk's crew naturally does. His ill-disciplined men have been led with their balls on a leash before, not because they were under a spell, but because that's what they do ("Man Trap").
What it perhaps the most closely resembles is being eaten inside by a Ceti Eel...
Timo Saloniemi