Here is a link to Zimbra's Documentation:
http://files.zimbra.com/website/docs...%20Install.pdf
When you install Zimbra on the addtional mailbox, you answer "Yes" to installing all the mailbox server components (store,apache,spell,convertd) and once you point it to your master LDAP server that pretty much links it all together.
One important thing to additionally address is the how access will work with a multi-mail store environment. You basically have 2 options. 1: Make all of your mail servers publicly available as mail1.domain.com and mail2.domain.com (you could round-robin DNS mail.domain.com to both). If a person logs into mail1.domain.com and their mailbox is on mail2.domain.com, they will get redirected on login and will be able to get their mail.
The second options is to install zimbra-proxy. Then that is the only box that needs to be publicly accessible (as mail.domain.com), and it will proxy all requests to whatever mailbox the user lives on