I'm not surprised that people find certain sets of instructions that would allow for them to penetrate another's personal space. Welcome to the internet. You can, in every sense of the phrase, dig up instructions to do anything. I know for a fact that everyone wants to be left alone at some point in their lives, whether it's once a decade or once a day. It's a small moment in time where it's just yourself and you. No one else around you matters, and it's necessary for most people. Some may need to sit with their own thoughts to remain sane. Others would need that time to just have some peace from a life that wouldn't otherwise know quiet. How would you isolate yourself so that your isolation remains consistent and uninterrupted? Perhaps read a book? Listen to some music? Well, that's too bad. There are instructions created for those entitled to your attention so that they can actually acquire it.
There is not a single instance where anyone would want to be spoken to if they are wearing headphones. There is not a single instance where navigating around that person's intentional isolation is justified only so you can get your flirt on. Wearing headphones/ear buds is one of the last and only indicators that shows a person genuinely does not want to be spoken to, along with burying their eyes in a book or a phone. People I know have told me that they would place headphones in their ears just so they could show those around them they don't want to be bothered. It's not always just a convenience; it can also be a deliberate mechanism to deter any outside confrontation.
For example, you can think that the woman you're sitting across from on the bus is attractive. That's a feeling you're allowed to have as an individual. You'd like to speak to her and ask her name, but she seems to be listening to music or watching a movie. You can infer this because she has headphones on and her eyes are glued to her phone's screen. What do you do?
If you decide that she needs to be distracted from what she's currently doing so you can have a conversation that she will most certainly feel bothered by carrying out, you are the kind of person that needs to rework their moral compass. Your ego does not automatically instill a right to bother someone else that clearly does not seek your company. It's not personal. They will not want anyone's company. You are not special and you are no exception simply because you find them attractive. Your urges do not justify intrusion into someone's personal space. Carry out your day just as she will. There is no shame at all in doing so.