I´ve done this last week.
Moved from SME 6.01-01 on P3 to SME7.1.3 on Dell PE1900!
What I did:
1) Installed 7.1 on PE1900
2) Used LAT (lazy admin tools) to backup configs (lat -dump) and restore on new server.
3) started Rsync daemon on old SME6 server
4) rsync from old SME6 to new SME7.1 on business time
5) tested everything
6) after hours I redid the rsync (very quick!) to get updated status
7) yum update on new SME 7.1 to go to SME 7.2

copy netlogon.bat from old to new server (domain controler!)
9) adjust configs (who´s domain controller, IP address, ...)
10) just to be sure, reboot and test everything again

Users just noted the new look of webmail and they have to create a new password... everything else was fine!