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.
(..) of a long and painful chapter for the people of Libya, who now have the opportunity to determine their own destiny as a battle rages in Libya's two largest cities. (..)2016 13 Hours