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Going by the definition of shows I never expected to be as good as I found them to be, I'd say:
Madoka Magica – When I heard about it being made, I only hoped that SHAFT could deliver me a Magical Girl show that wouldn't disappoint me, given how I got pretty tired of the genre at the time. When I watched the first episode, I thought it looked good, and had the typical weirdness I expected from a SHAFT work. it wasn't till much later on that the show really hooked me in, especially when fan speculation kicked into high gear. At the very least, episode 3 showed me that this wouldn't be your average, cookie-cutter Magical Girl show I've come to expect, but that it would be something much more serious.
Steins;Gate – I went in, expecting a typical sci-fi show and till about halfway through the series, I still didn't really think it was brilliant. Sure, it looked good, had likable characters and such, but when the show took a far more sinister tone, I knew this would be something I hadn't seen before.
Dusk maiden of Amnesia is a borderline case. Though I thought it was excellent, I already had high hopes for it before I started. I think it's because it has a similar element the aforementioned shows have: a somewhat laid-back, or even humorous surface, but underneath lurks a serious issue that becomes focal point halfway through, and it raised my expectations accordingly.
There are probably others, but these three stand out the most for me right now.
A lot of other shows I rated as high as these were great because of other reasons, and I wouldn't really call them masterpieces, just shows I really, really liked (like K-ON!! or Haiyore! Nyaruko-san).
Note that I don't call these shows 'perfect' (because I believe there is no such thing), but (to me) they are as close to perfect as humanly possible. There is usually at least one element I don't like (usually one or two characters), but if the sheer enjoyment I get from the show can make up for them, a show (despite its flaws) could still be a masterpiece to me.
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