I've had a number of people ask me how I managed to set up my iPhone to send and receive mail from my work account. My work uses Microsoft's exchange server to manage email. For security reasons, they don't allow folks to send mail unless they use either the official MS Web client or they're inside the firewall. They do, however, allow you to retrieve your email. This is the key that makes it possible to use your iPhone when you don't have official technical support.
You can set up a new account on your iPhone. For the incoming mail server, use your work settings. I prefer to use "IMAP" rather than "POP" because "IMAP" will synchronize with your exchange account and will also allow you to see any sub folders you may have created.
As for the outgoing mail server, you need to set up a free gmail account. Once that account is set up, you use the gmail outgoing or "SMTP" server. Gmail will allow you to set the "reply to" address to your work address, so to all appearances, when you send email, it comes from your work account.
I haven't included the details here, but this is the basic idea.