I'm not sure if the issue is not really with the SSL certificates. Your mail server certificates might have expired or changed. Alt-F ships with a set of really old certificates. But that might be another issue.
To solve the problem at hand you can
1-put the "tls_starttls off" directive in the /etc/msmtprc file and do not use the Mail Setup webUI afterwards. You can test mail by just typing "echo Ello | mail -s "Test" you@yourserver"
2-edit /usr/www/cgi-bin/mail_proc.cgi and insert the "tls_starttls off" at around line 56, as in
echo "
tls_trust_file /etc/ssl/ca-bundle.crt
syslog on
host $host
tls $tls
tls_starttls off
auth $auth
from $from
aliases $CONFA" > $CONFF
This hard-codes that directive in the configuration file, you can add or remove a leading '#' to the line to experiment with/without it.
Before doing the above edit, execute the following commands:
aufs.sh -n
mkdir -p /Alt-F/usr/www/cgi-bin/
aufs.sh -r
Let me know if it works.
Cheers!
sm