Once you have postfix started (either using the init script or by executing 'postfix start') you should be able to send messages from any MUA that is configured to use that system as the outbound SMTP server. You may want to check your postfix configuration (for simple syntax errors) first by executing 'postfix check'.
It is always a good idea to check the logs (under the /var/log directory usually) for any messages if you have any problems. If things seem to be working, you can check to see if postfix is listening on port 25 correctly by using the command:
netstat -an|grep :25
and ensuring that there is an entry that looks sorta like
tcp 0 0 0.0.0.0:25 0.0.0.0:* LISTEN
The postfix documentation is available online @
http://postfix.behrsolutions.com/ if you need more information.
As for receiving email, you will need to install/configure some type of POP or IMAP program if you want Windoze systems to be able to retreive messages.