Though if your trying to reduce your maintenance window you can technically go from 5.0.14 > 6.0.6 (backup of course).
Saying 'go the latest on the minor version first' has just become the common practice since it's easier than remembering the upgrade paths chart:
4.5.0 - 4.5.6 > 4.5.11 > (
LDAP replica step) > 5.0.2 - 5.0.23 > 6.0.0 - 6.0.6 (
LDAPs note)
You should also consider Debian5 at some point for longer support past 6.0 (and 64-bit for even longer) - though I see your profile also mentions an Ubuntu8 64 system already.