They made it 'painfully' obvious/clear that we were not welcome. [=they made it very clear in a way that was rude or upsetting that we were not welcome]
His ankle is swollen and 'painful to the touch'. [=his ankle hurts if he touches it]
After the injury she was 'painfully' aware that her career in tennis would be over.
(..) And I think that's what we all find most astonishing, is that this girl was adored in the Capitol. And I think for you, Peeta, it must be particularly painful. I wish I could give this rose to you, Katniss. He's changed so much already. What are they doing to him? A sweet gesture for a girl (..)2014 The Hunger Games: Mockingjay - Part 1