postconf -e "relayhost = [myrelay.fqdn]"

It can’t hurt to make sure you have the right setup. Here’s what I have on one of my rhel6 systems 

alternatives --display mta
mta - status is auto.
link currently points to /usr/sbin/sendmail.postfix
/usr/sbin/sendmail.postfix - priority 30
slave mta-pam: /etc/pam.d/smtp.postfix
slave mta-mailq: /usr/bin/mailq.postfix
slave mta-newaliases: /usr/bin/newaliases.postfix
slave mta-rmail: /usr/bin/rmail.postfix
slave mta-sendmail: /usr/lib/sendmail.postfix
slave mta-mailqman: /usr/share/man/man1/mailq.postfix.1.gz
slave mta-newaliasesman: /usr/share/man/man1/newaliases.postfix.1.gz
slave mta-aliasesman: /usr/share/man/man5/aliases.postfix.5.gz
slave mta-sendmailman: /usr/share/man/man1/sendmail.postfix.1.gz
Current `best' version is /usr/sbin/sendmail.postfix.

I’d stick with using the postfix command, but if you’re scripting or some such, the setting is in the /etc/postfix/main.cf file. All the command seemed to do is append the file, but I’m sticking with the command to be safe rather than sorry.