Sounds like an ear infection starting. We've had many. My kids have tubes.
I would go in and have it looked at. One time my son's was quite bad and he was in misery. They can get quite bad pretty quickly so keep an eye on it. If he's just complaining it's sore, it's probably not that bad yet. You may or may not have to go on antibiotics. Not all pediatrician's like to give antibiotics - my kids typically always needed them though because ours is did not get better on their own.
For pain, we were advised to alternate between Tylenol and Advil so that the pain relief never wore off. So if you gave Tylenol then you'd give a dose of Advil in between the next dose of Tylenol , never more than the recommended amounts of each per day. But our pediatrician and pharmacist advised that - best to check with your doctor's office. They should at very least have someone on call on weekends for emergencies. I'd give them a call.
My kids with tubes would have stuff ooze out of their ears - that was the tubes working. I'm not sure if stuff is visible without tubes .. but there may be some discharge. We had drops (from the pharmacy, but prescribed by doctor) for that. I would think at very least, if you didn't get antibiotics, you'd want something to treat it. But you'd need a prescription.
Good luck :) I know it can be painful and distressing - best to call.