It matters because select will have to iterate over all the file descriptors you passed to it, while kqueue for example have knotes registered to it when it wakes up and won't need to iterate over everything, but just the knotes it got. Not to mention the data copying from userland to the kernel in case of select/poll.
Back to the request rate limitations, the limitation is mainly coming from the # of system calls you can execute in a sec (accept() in this case) which is heavily influenced by the context switches.
Looking at the application CPU gives you a very good idea of what your bottleneck is. If your CPU is 100% then it's clear your application is hitting the limit, but if the application CPU is at 30% and you cannot process more requests / sec then you've hit the system limit here.