If we’re talking about vintage clothes, I can usually tell what’s pricey (although not always). More contemporary stuff, no, since a lot of it is about whether a label is premium, or whether I can recognize that a specific item is limited edition. It’s pretty advanced in-group signaling which I don’t find useful since I’m not in those groups.
On the whole, I’d say I’m reasonably good at the over/under, but not rankings. In other words, if you give me a bunch of different variations of whatever and ask me to divide them into the pricier half and the cheaper half, I’m going to be able to do it with few errors. But if you ask me to pick out the one most expensive thing, no. Odds are good I’ll pick the second or third most expensive thing.