"Though" (or more often, "although") at the beginning or middle of a sentence is a conjunction, like "and," "or," "but," or "so". It connects two halves of a sentence across a comma.
"I like him, (al)though he doesn't like me."
"(Al)though he doesn't like me, I like him."
"Though" at the end of a sentence is a "conjunctive adverb", like "however" or "nevertheless". It connects two different sentences across a period.
"I like him. However, he doesn't like me."
"I like him. He doesn't like me, though."
When we use "though" at the end of a sentence, it usually means that the sentence is a "second thought"---first, we make a strong statement in the first sentence. Then, after we have said the sentence, we realize that there is an important exception, and we mention it with "though."
"I'm the fastest runner in my company! Everyone else in my company is over 80 years old, though. I guess my achievement isn't actually very impressive."