-Pick a backup method out of:
Open Source Edition Backup Procedure - Zimbra :: Wiki Rsync, cp, lvm, snapshots, disk image etc, and there's tons of other FOSS backup methods listed throughout the forums.
-I would stop off at at least
4.5.11 before making the jump to 5.0.6, as there's lots of tomcat & ldap changes around 4.5.6/.7 to account for (.6 has a clamav bug though that can be tricky on mail delivery).
-Read the
4.5.11 release notes
-Upgrade to 4.5.11
-Verify your 4.5.11 works
-Make another backup (you got this far, might as well not go all the way back to 4.5.4 if something goes wrong to the jump to 5.0.6)
-Read the
5.0.6 release notes
-Upgrade to
5.0.6
-Test & relax if all went well
Should you have to revert you'll need to clear your /opt/zimbra > copy in the backup > run the
4.5.4 installer (or if restoring the 4.5.11 backup it's installer)