和 sets the two level in a shared act; 跟 can also mean follow at the heels, trailing behind one party. For plain togetherness either works; for following, only 跟.
妹妹很喜歡聊天和爸爸。 ✗ → 妹妹很喜歡和爸爸聊天。 ✓ (和 + person goes before the verb)
我和你看電影 said as two separate watchers ✗ → 我和你一起看電影。 ✓ (one shared activity, not two)
我說和他 ✗ → 我和他說。 ✓ (跟 fits this better: 我跟他說)
English 'with' trails the verb (chat with dad); Mandarin 和 leads it (和爸爸聊天). The English speaker reaches for the end-position and lands 和 in the wrong slot.