Tallahassee - S2-E6
Revealing mistake: When Hook and Emma are climbing up the beanstalk, as Hook remarks, "First beanstalk?", you can see that Colin O'Donoghue is actually gripping the vine with his left hand, which is covered up by his sleeve; the hand that was cut off. (00:08:50)
Tallahassee - S2-E6
Revealing mistake: When Neal is being chased by August, he runs on top of a car before attempting to jump the fence. Just before he jumps on top of the car, you can see that the one who actually performs this action is Michael Raymond James' stunt double. (00:26:40)
Answer: He knows who she is because he knows that the fairy tales are true. He was also shown to sneak out to go see Emma or someone else. Sometimes he succeeded, sometimes he didn't. This is how he knew to look for her despite his strict mother.