I would say the opposite is true for, because being ambushed is a rare case in my experience. Maybe it's because I play a high sneak/high perception character but I'm rarely ambushed and when I am, I'm usually expecting it (like coming out of the elevator in Trinity Tower). I'm not much of a chem user myself but all the combat based ones are potentially beneficial to me since I usually know when I'm going to be in combat and what I'm going to be facing. I could see the benefit of choosing to enhance perception if I'm going to be taking on a sniping battle. And in addition to barter, there are certainly times when you kind of know that you're likely to get in to a persuade check situation. I'll agree that there's not a lot of situations where I know in advance I'm going to want to enhance intelligence.
Besides, skill enhancing apparel is essentially the same as the chems. I don't wear Reginald's Suit all the time just in case I need a charisma bonus.