1. "Emissary" - first by a mile. Does a good job of establishing characters, setting, the Bajoran/Cardassian conflict, etc., while at the same time being just a good sci-fi story.
2. "The Cage" - presented a fascinating narrative and several interesting characters (who didn't stick around except for Spock, unfortunately).
3. "Caretaker" - a good story overall in concept, but uneven in execution, with some glaring logic holes. More good than bad, though. As for the characters: about half of them make a good first impression, the others... eh.
4. "Encounter at Farpoint" - this episode is horribly dated by when it was made; the production values are not very good, the music is cheesy, some of the dialog is way over the top (especially with this version of Troi, who feels everything she senses, which made every scene with her almost embarrasing to watch), etc. But at it's core, there is still a fairly interesting story here, and most of the characters come off well.
5. "Where No Man Has Gone Before" - decent story, but just kind of... there. Nothing about it jumped out at me, unlike with "The Cage". An ok pilot, but nothing special.
6. "Broken Bow" - bloody AWFUL. Last place by two miles. Almost ok story riddled with HUGE plot holes, and not a single main character that rises above "They're... tolerable, I guess." If I could go back in time and tell myself not to bother watching this, I would.