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You need to fire nails into a heavy target (like pinky rider or stronger) until they have enough in them that the nails glow. Then you can throw the shield or shield bash into the demon with the nails sticking out of it and the nails will all fly out of the target and do damage to any nearby demons.
It needs to be a heavy demon because the fodder demons will die long before they have enough nails in them to be primed to explode.
The biggest issue is making sure you do it to the heavy when there are other targets around. Any target damaged by the area of effect from the burst of the nails flying out of the demon will give you a point towards the mastery, so you can get a bunch of points at once if there's a lot of nearby demons to your target.
If there's a lot of fodder nearby it is best to use the shield throw instead of the bash as the area of effect damage from the bash's shockwave might kill some of the secondary targets you're trying to use to get the mastery points.
Hope this helps!