Undoubtedly there are people who can hear their equipment or cables break in. To me however it stays a mysterious phenomenon.
Take a cable ... it has no arrows on, it has no direction. And audio is an AC signal so there’s no direction there either. That can’t have anything to do with it.
Chemical properties ... they could change over time. Yes, that can be a reason. But hey ... we’re talking about copper, or silver, or gold, not much to change there. And even if so, I always ask myself how come after the first 100 hours the sound always gets better? Statistically chances would be 50 / 50 that the sound gets worse ... I never hear someone about that. Just a fun fact.
Could it also be that it is a strategy to give oneself peace of mind? Suppose someone just bought expensive cables and ... oops ... there’s no clear audible difference with the old ones. Oh ... wait ... yes ... after 100 hours of breaking in they sound a lot better. Saying that to yourself will make you feel better, even if no one else hears what you hear.
Wait ... my new USB3 cable just broke in ... o yes, the picture on my PC monitor is much clearer now!