Define "good"
The problem is that a question like this cannot be answered how you desire. Yes, the RoCoo P is a high-end player, but may not be exactly what you are going for depending on genre. I am not very familiar with the RoCoo P's faults and praises, but i can talk about the M50S's.
The M50S's are the Straight-cabled variant of the M50's, which many people like.They do however have a reputation for their bass response. Some people may not like how bassy these headphones are.
Depending on your music tastes, you may opt for a different set of cans for the job. If you like bass heavy music, then the M50S's may be a good choice for you. However, if you don't care for much bass, you may wish to find something else or at least look at reviews of what people say about them.
In a bit more basic terms and to conclude, most audio equipment has its pros and cons, and the type of music you listen to may or may not excel on any rig you have. This is why many people have multiple types and brands of headphones, IEM's, etc...as well as multiple different amplifiers, DAC's, and other equipment used for playback.
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RoCoo P with ATH M50S...is this a good setup for a new audiophile? If not, any suggestions?