BAT Coven: My first "boutique" pedal was a Black Arts Toneworks Coven, a colorsound OD combined with a Muff fuzz. Up until then I'd had a TS9, SD-1 and maybe something else.
I was trying to compensate for dinky little amps at low volume. That pedal was revelatory (instant Doom! Drop D! Sabbath!) - and led me to buy all sorts of ODs and fuzz boxes that are on my shelves - AmpTweaker, Spaceman, Analogman, Wampler...
The Coven is still in the signal chain. One of the LED's is now dodgy, so I'm considering buying another.
But it really led me to start thinking about better amps. Black Arts Toneworks pedals and Orange amps = goodness and much fun.
EQD Dispatch Master: see the above comment in the thread for an excellent description of it. As with my comment above, this led me to buy all sorts of delays and reverbs - Avalanche Run, Afterneath (v1 and 3), Transmisser(!), Polymoon, Mercury 7, Reflecting Pool, Volante, Timeline, Cloudburst... All of which are great and I mostly use the Volante today, but the Dispatch Master has something very sweet nothing else quite has.
Strymon Ultraviolet: bought on a whim when I had some extra cash from a trade-in deal on a couple of guitars and amps. I had no idea I like Vibe and now love it.