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I really enjoy tinkering with my hardware. Having grown up in a place where cars where in the front yard on blocks I have the equivelent in my living room with PC's.
I'd first start by getting a good case and power supply. A good power supply is less likely to destroy your components, be queiter and run cooler, less likely to be ea fire hazard or to zap you and have more and longer connectors for things like fans, hard drives, and whatever else you put in.
Next, you should get a case that has thumbscrews or some eeasy way to "pop" everything open...like esliding doors , easily removable front bezel etc. Because when you open up your case all the time you want it to be easy. Plus the more screws you have the more contrived the bezel is the more likely you are to wreck something or bend something and have to get a new case anyway. I also go for the light aluminum ones just becausue they are easy to move around, have soft carners and keep cool.
Aother thing about getting a good case is that all the misc supplies like mobo screws and risers are prorvided. The first PC I built from scratch had no risers and no screws so In had to make do with nylon twist-ties and antistatic bubble wrap underneath.
What kinda hardware? IMO if you get into this you are gonna be buying alot of it anyway, so start however you want. I got one case/PS set up filled with "high end" stuff and another one filled with the stuff I took out of my "high end" computer to upgrade it. the stuff I take out of my "low end computer gets put in a salvaged case and sold or given away...But if you are worried about screwing gsomething up at first go low end on everthing just to buid it and gain confidence, then later swap everything out and start getting better stuff.
If going high end, be sure to research your mobos and get a good one with a good warrenty. Buy a anti-static wrist strap to just in case.
If going dual processor, get a case and a Power supply for that task. If you don't know, get a case and a powersupply for dual processor anyway in case you change your mind.
Just remember the point is to makae your hardware as flexible and easy to manage as possible.