Documentation for JIRA 5.0. Documentation for other versions of JIRA is available too.
The "Unable to relay" error means that your mail server doesn't allow relaying for the e-mail address that you are using for your SMTP server. (see http://www.chilkatsoft.com/faq/Smtp550.html). Please try getting your mail server admin to enable relaying for your e-mail address or use another address that has relaying enabled.
You can get more help on changing the e-mail addressed used by JIRA here.