Don't be afraid of electricity! If you're working on voltages of 50v or less (as most of us are most of the time) its virtually impossible to get a shock or kill yourself (I'm told licking the top of a PP3 is painful, but I've never been stupid enough to try it!). I guess if you impaled yourself with some electrodes near the heart and attached 50v to it you might kill yourself, but if you're doing that then you have more problems than the risk of electric shock!
You can get burns if your skin is too near when you short out a high current source, so its worth being careful with high power battery packs (NiCd, LiPo etc) but if you are reasonably cautious then you've really nothing to worry about, aside from damaging expensive equipment.
High voltages and Mains are a different matter, and you should assume that they are "live" or capacitors fully charged until you have proven positively to yourself they are not.
If you're using a multimeter with insulated probes and you know what you are trying to measure then you are perfectly safe. I've done a LOT of mains work (250v and 400v AC) and have never received a shock using a multimeter on live wiring because I take my time and make sure I use good quality probes and wear gloves when reaching through chassis to get to the point I'm measuring!