Ace has never demonstrated Armament Haki or Observation Haki. We can make all the assumptions we want, but the fact is Oda never showed him using it, so we don't really know and can't say he can use it. Even if Haki didn't turn your arm black pre timeskip, Oda would usually do something to show someone was capable of it, like someone would comment on them knowing it, allowing the person to hit and harm a logia user or Luffy, or something like that. It's not hard for me to believe because I'm pretty sure he was introduced before Haki was truly integrated into the series, so Oda had to keep him somewhat downgraded otherwise he would have created some issues in his past fights. Same with Crocodile. If Crocoboy knew Haki, he would have thrashed Luffy. If Ace knew Haki, he probably would have been able to take down Teach, who is a character who should also know Haki. He knew about it, but not how to use it. But seeing as he had the Yami Yami no Mi, that makes Armament Haki, at least against DF users, redundant.
Anywho, as for the topic, Ace would win anyway because he was stronger than Smoker. Their fruits may have cancelled each other out, but I'm pretty sure Ace could of just physically stomped a hole into Smoker.