If the concerned application uses a (permanent) specific port for P2P communication, it can be blocked by creating a new firewall rule on the SEP clinet. please follow the article at the below link on how to create firewall rules in standalone SEP clients.
Firewall policies on unmanaged Endpoint Protection clients
http://www.symantec.com/docs/TECH105725
But, if the users can change the port used by the application for P2P communication, then blocking just one port will not be effective. In such cases, its to better to create 2 rules as follows asnd place them at the top of the list in the same order.
Rule 1 - To Allow traffic from "application.exe" on specific port that the app uses to communicate with "server".
Rule 2 - To Block ALL traffic from "application.exe".