What rear derailleur do you have? The stock long cage Ultegra? If so, it's probably the same one I have (my bike is '07 vintage, not sure the model number), and all it takes is a little tweak of the B-screw and I'm set. The 27T cog makes all the difference in the world on those long hilly steep rides. I don't even have to readjust my cable, though YMMV on that.
(But, plan on replacing the whole cassette. You *might* be able to find the right cogs at a swapmeet, but Shimano doesn't sell individual cogs, or actually, the lower gears come fused together anyway.) They're easily swapped out so if your 12-25 isn't worn out, you can keep it for your flatter rides.
Can't help you on the suicide brakes. Were they added on to the bike? Trek's archive says your bike should've come with R700 brifters (also same as mine).



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