What's the best way to check if an SMTP server is SSL-enabled or not?
That depends whether you mean SSL or TLS.
SSL has it's own dedicated port at TCP/465. The best way to test for it's presence would be to use OpenSSL's wonderful s_client which will negotiate the SSL trickery for you.
openssl s_client -connect localhost:465
If your server isn't bound to localhost then obviously replace that with the IP or hostname.
TLS looks just like normal SMTP at first. The encryption is negotiated from and on-top of the plain-text protocol. You can test whether it is available by issuing an EHLO request to the server. You can use Netcat or Telnet clients for this.
$ nc -v localhost 25 localhost [127.0.0.1] 25 (smtp) open 220 mail.example.com ESMTP Exim 4.69 Fri, 11 Sep 2009 09:25:20 +0100 ehlo test 250-mail.example.com Hello localhost [127.0.0.1] 250-SIZE 10485760 250-PIPELINING 250-STARTTLS 250 HELP
The important line is second from last which advertises the STARTTLS capability.
In order to say how to enable SSL/TLS for your mail server you'll need to tell us what mail package you're using.