Still being new to this, I'm in sort of an "anything goes" sort of mode, but here's my ritual when it comes to trying something new.
I've been trying to not re-buy bottles I've tasted, but instead gather as many different ones as possible and try each one. So......
I typically read the bottle's label all over a few times to get acquainted, then unscrew or uncork it (although I am anti-cork, I still attach a stigma that screw top bottles are not as good as corked bottles -- VSOF proved me wrong). I smell the cork -- just for fun -- I've never really been able to discern anything from this. Then a small pour neat -- similar to being served the first sip of wine in a restaurant -- swirl it, smell it, down it. Mmmmmm.
Then, the serious, two-finger pour, also neat. If I dig the whiskey neat, I continue to drink it that way until I....A) have a pour that isn't up to par or B) get bored. At this point I might add a splash of water.
I, typically, like to add water to soften the texture of the whiskey, not to "bring out the flavors." Although I do understand this concept (similar to adding salt when cooking, no?), I feel that most of the time I can taste as well neat. If the whiskey is still not to my liking, I may add a rock or two.
There are very few bourbons that I prefer with water or rocks, but since I have nothing to lose, I like to be thorough and explore all of my options. My exception to the "Neat Rule":
Baker's - I like with a splash of water sometimes -- it seems to create a velvety texture I can't resist.
J.W.Dant BIB - gotta have some ice in this one....whoa...too sweet
WLW SR - I like to keep this one in the freezer
Beam White & WT101 - I like these on the rocks if I'm also drinking beer -- I find the bourbon scours up my mouth and really bring out the flavor of a good micro.
What I would like to add, but can't quite get, is what will help me cleanse my palate in-between tastings?