Scenario
You current boot order is OS drive first, it's set at this this to give you the quickest boot time as it skips trying to boot from the optical drive and usb flash drives, or any other hard drive for that matter.
You get a problem and you decide to check the RAM using memtest 86.
This involves burning an ISO to an optical disc and then booting to it.
You insert that disc into the optical drive and find you can't boot to it because your boot order is optimized for boot speed (skips optical drive)
This is where "boot override" comes.
This allows to boot from that optical drive this one time without having to reassert your quick boot order for future boots.
You can also use it to install operating systems and test Linux live discs.