I found some information on configuring Postfix to provide SMTPS (SSL/TLS) services on CentOS 5.1 Server Setup: LAMP, Email, DNS, FTP, ISPConfig (a.k.a. The Perfect Server) – Page 5 and Getting Postfix to run SMTPS on port 465.

The first article suggests main.cf configuration settings such as:

postconf -e 'smtpd_sasl_local_domain ='
postconf -e 'smtpd_sasl_auth_enable = yes'
postconf -e 'smtpd_sasl_security_options = noanonymous'
postconf -e 'broken_sasl_auth_clients = yes'
postconf -e 'smtpd_recipient_restrictions = permit_sasl_authenticated,permit_mynetworks,reject_unauth_destination'
postconf -e 'inet_interfaces = all'
postconf -e 'mynetworks = 127.0.0.0/8'

postconf -e 'smtpd_tls_auth_only = no'
postconf -e 'smtp_use_tls = yes'
postconf -e 'smtpd_use_tls = yes'
postconf -e 'smtp_tls_note_starttls_offer = yes'
postconf -e 'smtpd_tls_key_file = /etc/postfix/ssl/smtpd.key'
postconf -e 'smtpd_tls_cert_file = /etc/postfix/ssl/smtpd.crt'
postconf -e 'smtpd_tls_CAfile = /etc/postfix/ssl/cacert.pem'
postconf -e 'smtpd_tls_loglevel = 1'
postconf -e 'smtpd_tls_received_header = yes'
postconf -e 'smtpd_tls_session_cache_timeout = 3600s'
postconf -e 'tls_random_source = dev:/dev/urandom'

postconf -e 'myhostname = server1.example.com'

And the second article tells how to modify master.cf to enable SMTPS:

smtps     inet  n       -       n       -       -       smtpd
  -o smtpd_tls_wrappermode=yes
  -o smtpd_sasl_auth_enable=yes
  -o smtpd_client_restrictions=permit_sasl_authenticated,reject