Its really a joke what marketing has done to the audio world (and I love my audio gear, including many headphones). Most has been covered already in this thread but the statement below needs addressing.
My PC soundcard (Asus Xonar D2X) can be switched between 16/24-bit and 44.1KHz - 192KHz sampling, and I honestly can hear A difference, but I'm not sure I'd say it's better, just different. Furthermore the qualitative differences in settings changes between songs, so I wouldn't be surprised if it's not at all the sampling rate and bit-depth that I am hearing as much as different paths along the circuit having different noise floor's etc.
One thing that makes a HUGE improvement in audio quality is to use ASIO instead of the default Windows audio kernel.
The reason you can hear a difference when changing the sampling rate inside your OS is that you most likely are changing volume from within Windows. Software volume control works by 'stealing bits' from the digital signal before converting it to analogue. If you were to set you windows volume panel to 100% and use an external device (i.e. a headphone amp or anything of quality with a volume pot) to change the listening level, you would be hard pressed to hear a difference.
As far as ASIO, absolutely good stuff. I use WASAPI as I've had more success on various systems when ASIO was just being a plain old PITA. I assume you're using foobar?
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