Vanc doesnt cross the GI barrier, so if taken IV, it wont get into the lumen to clear the infection. Conversely, taken orally, it won't get out into the blood, which curbs side effects.
With severe C diff when there is constipation, sometimes you worry that the PO stuff won't make it to the site so you will treat with PO vanc + IV metro.
btw they don't use vanco now a days because of the resistant strains that developed against it. though metronidazole it self cause C. diff collitis but as it doesn't cause resistance so it is the preferred and used drug.
Vanc is always given IV because of poor oral bioavailability. But as an above poster said that's a good thing if the infection you're treating is in the gut and that's where you want the drug, which is why it's oral for pseudomembranous colitis.