1.

chkconfig is a perl wrapper to insserv, which actually mimics chkconfig very well.

linux-kaf2:~/Desktop # chkconfig -l | grep multi
multipathd                0:off  1:off  2:off  3:off  4:off  5:off  6:off
linux-kaf2:~/Desktop # insserv multipathd
linux-kaf2:~/Desktop # chkconfig -l | grep multi
multipathd                0:off  1:off  2:off  3:on   4:off  5:on   6:off
linux-kaf2:~/Desktop # insserv -r multipathd
linux-kaf2:~/Desktop # chkconfig -l | grep multi
multipathd                0:off  1:off  2:off  3:off  4:off  5:off  6:off
linux-kaf2:~/Desktop #

2.

what insserv/chkconfig actually do

refer runlevel5 as sampling:
linux-kaf2:/etc/init.d/rc5.d #
linux-kaf2:/etc/init.d/rc5.d # ls -l | grep multi
linux-kaf2:/etc/init.d/rc5.d # insserv multipathd
linux-kaf2:/etc/init.d/rc5.d # ls -l | grep multi
lrwxrwxrwx 1 root root 13 Nov  9 10:52 K01multipathd -> ../multipathd
lrwxrwxrwx 1 root root 13 Nov  9 10:52 S04multipathd -> ../multipathd
linux-kaf2:/etc/init.d/rc5.d # insserv -r multipathd
linux-kaf2:/etc/init.d/rc5.d # ls -l | grep multi
linux-kaf2:/etc/init.d/rc5.d # chkconfig multipathd on
linux-kaf2:/etc/init.d/rc5.d # ls -l | grep multi
lrwxrwxrwx 1 root root 13 Nov  9 10:53 K01multipathd -> ../multipathd
lrwxrwxrwx 1 root root 13 Nov  9 10:53 S04multipathd -> ../multipathd
linux-kaf2:/etc/init.d/rc5.d # chkconfig multipathd off
linux-kaf2:/etc/init.d/rc5.d # ls -l | grep multi
linux-kaf2:/etc/init.d/rc5.d #
linux-kaf2:/etc/init.d # ls -lt
total 672
-rw-r--r-- 1 root root   783 Nov  9 10:54 .depend.boot
-rw-r--r-- 1 root root   563 Nov  9 10:54 .depend.halt
-rw-r--r-- 1 root root  1115 Nov  9 10:54 .depend.start
-rw-r--r-- 1 root root   665 Nov  9 10:54 .depend.stop
drwxr-xr-x 2 root root  4096 Nov  9 10:54 rc5.d
drwxr-xr-x 2 root root  4096 Nov  9 10:54 rc3.d
drwxr-xr-x 2 root root  4096 May 30 10:54 rc2.d