Were you using stunnel before? If not, it wont' do anything. I assumed you were running Stunnel to provide secure SMTP and secure POP3, because I've seen that error message generated before as a result of stunnel.
If so, for SMTP, you should run:
/usr/sbin/stunnel -d smtps -l /usr/sbin/smtpd -T
It appears your stunnel configuration is incorrect, with respect to the "-d smtp" flag as well as the "-T smtp". It appears "-d smtp" is your root cause because you are causing stunnel to listen on TCP 25, instead of 995.
Perhaps you should re-read
http://kepler.covenant.edu/~talarson/ssl/SSL-Email-HOWTO.html Hope this helped,
Nathan