You can say, caffeine works most effective towards about the same parts of the heart that are sensitive towards
adenosine. In other words, the atria, the AV node
and to a certain degree the RVOT (where I assume from another post that your PVCs did origin). Caffeine is an adenosine antagonist, which means the caffeine blocks those receptors (which is why people drinking a lot of coffee complains that their SVT is hard to convert with adenosine, there are a couple of those posts here).