The order of the pppoe rc script is wrong, relative to other rc scripts. pppoe has # chkconfig: 2345 80 20 For example, ntpd has # chkconfig: - 26 74 ntpd will be started before pppoe and will fail. Basically pppoe should start before ALL other services which depend on a live Internet connection.
It's fixed in rp-ppoe-3.0-3. You will find it in the rawhide.