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Although Dortmund has better experience in the Champion League compared to PSV, but I think it still does not fully guarantee for Dortmund to be able to beat PSV . Indeed, Dortmund are in the hell group in the group stage but still, PSG and Milan also have a performance that is not completely stable at that moment. With this factor, then I cannot assume it is entirely possible about Dortmund being better than PSG and Milan.
After all, in this season the fact is that PSV also has very good results in the Eredivisie, because PSV managed to win all its matches in the first half of the season. Indeed, the results of matches in the domestic league cannot be fully used as a benchmark for their performance in the Champion League. But yes, at least with the good results PSV has in the domestic league is likely to make PSV's morale also remain good in the round of 16 against Dortmund later.
I think Dortmund have different mentality this season. They are good in Champions League, but scrumble in Bundesliga. They may still be carrying on the effect of last season failure. They look uninterest in the Bundesliga, but full motivated in Champions League. Dortmund have a better experience in the Champions League compared to PSV if we just count the latest Era, because PSV also have proper history in Champions league, but past experience alone doesn't guarantee success in a specific encounter.
PSV have a stable morale with doing excellent results in the Eredivisie and progressing to the round of 16. This aspect of them is better than Dortmund's, but the Champions League is a different competition with its own dynamics. No body had thought that Dortmund would do good at a tough group stage. I think Dortmund will show their best in Champions League to compesate their performance in Bundesliga.