Heat the oven to 400°F. Cut 1/4 inch from the top of the garlic head to expose the cloves, drizzle with oil, wrap loosely in foil and roast for 40 to 45 minutes until the cloves are soft and golden. Cool for 5 minutes and squeeze the cloves into a bowl.
Meanwhile, place potato chunks in a steamer basket over 1 inch of simmering water. Cover and steam for 20 to 25 minutes until the largest piece breaks easily under a fork, checking the pan does not boil dry.
Warm buttermilk gently in a small saucepan over low heat until just warm; keep it below a simmer. Transfer hot potatoes to a dry bowl.
Mash potatoes with roasted garlic and butter by hand until no large chunks remain. Fold in warm buttermilk a little at a time with salt and white pepper until fluffy and spoonable.
Transfer to a warm serving bowl and serve immediately, smoothing the surface with a spoon rather than beating the potatoes.