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You can use a client (Thunderbird, Outlook etc) that can be configured for secure smtp and secure pop and try to send/receive mail through that server..
Apart of that to test secure smtp, you can telnet to the mailserver on port 25 , use "ehlo" and see if supports STARTTLS. For secure pop, the only thing that comes into my mind, is to verify that the server listens on port 995 (secure pop3 port).
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