RE: The My Little Pony: Friendship is Magic Not-Clan: 20% Cooler Than Official Clans
Every episode has its ups and downs, and you will like some episodes more than others depending on who you feel is best pony.
The first two episodes of season one must be watched because they introduce the mane six and set the stage for the rest of the season. After that, you can really watch any episodes you like and get a very general idea of what the series is like, but it's best to at least watch episode three because it sets up the Grand Galloping Gala. Episode four is really the first true example of how the series works as a whole, but if you don't at least watch the first two episodes you won't properly be introduced to the series.
The problem is that while the first two episodes are fantastic for introducing people to the series, they are terrible at bringing people into the herd. I believe Equestria Daily showcased a poll that was done on which episode was best for bringing new people into the herd, but I don't know what it was. Probably Sonic Rainboom or Winter Wrap Up or one of those other popular episodes.