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.
(..) You're not gonna fuckin' die, kid. All right? Listen to me. You're gonna be fine. Along with the kneecap... the gut is the most painful area a guy can get shot in. No shit! But it takes a long time to die from it. I'm talkin' days. (..)1992 Reservoir Dogs