The route command has nothing to do with the situation. Route commands manipulates the routing table as you have two or more interfaces connected to different networks, or specific routes are accessible by other gateways rather than the default. Then you use route command to introduce these routes as your computer normally uses standard IP forwarding routing and doesn't know how to obtain the alternative routes, since it normally doesn't use routing protocols.
In your case, as you sit in a cafe, it has one default router and no other means to communicate with Internet. VPN implies tunneling connection trough some encryption, you may suspect that port 22 is blocked by the router but port 25 has nothing to do with it (even if it is blocked as you connect trough VPN) if your computer connects to VPN because it does not connect to the mailbox explicitly. It is also possibility that it is blocked by router one level above the router in cafe as it may be part of their internal policy. "UNIX Essential and Core" DVD explains this stuff.