Season 2 might feel "better" but it's more self-referential. In Lesson Zero for example, Twi has a breakdown because she hasn't produced her weekly letter. This has more meaning when you've seen Twilight acting normal (this is true of all the "breakdown" episodes, they're about seeing someone act out-of-character, which is meaningless if you don't know the character they're being out-of), and when you've seen Twilight actually send a new letter every week.
I don't think it's a good idea to deviate very far from the production order. People said the intro episodes weren't a good intro because they were two-part adventure while the rest of the episodes were slice of life, but then they made more two-part adventure episodes. Now people sort of complain a bit because the Nightmare Moon eps weren't as good as the Discord or Royal Wedding eps, but those weren't designed to be an introduction, Nightmare Moon was.
For the regular episodes, you can mix them up a little without harm (some shouldn't be mixed), but I don't think it's a good idea to front-load all the "good" episodes for someone to try, and get an unbalanced look at the show. And then there's always a matter of taste, and if you try to give someone "good" episodes and keep the "bad" away, they might actually like the bad more than the good, so you might be causing the opposite of the effect you intend.
IMO, the best idea is just to put the show out there as-is and let it be judged for being itself. It's also a good idea to tell people how the tone changes after two episodes, so they're likely to give it more of a chance.
Also I should mention that Jayson Thiessen has said that he worked pretty hard on giving the show a faint sense of continuity, so it's episodic, but if you watch it in the order it was laid out, there is a slow progression, and characters slowly change and learn, even if it doesn't look like they changed or learned anything.
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