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.
(..) Lady Litton, listen to me. I have- I have deceived you. I am not Guy Gadbois. I am Inspector Clouseau of the Sureté, and it is my painful duty to arrest you. Do you know my husband? Yes, I must confess I do. I met him several years ago. When I meet him again I shall arrest him (..)1975 The Return of the Pink Panther