For quick and dirty diagrams, I use LTspice. It's fast, relatively easy to make new parts, and I'm familiar with it. Also, I often make diagrams from simulations, so it's a matter of cleaning something up for documentation, presentation, or publication.
If I want really nice looking, simple diagrams for explaining concepts in presentations or publications, I have found Libreoffice to be a good tool. I have done this for many years. I have set up a template with a 1 cm grid, and have a library of parts for such diagrams. Some benefits of this approach include import and export of many formats, both vector and bitmap, inclusion of photos and other graphic elements, multi-page documents if you want several version of a diagram, or if you want multiple figures in one file. There have been some gotchas and glitches over the years, and it's not perfect, but it works for me. I can paste EMFs into Word (a god-awful, terrible, horrible, buggy POS) or Powerpoint (actually ok), or generate PDFs for use in LaTeX.
I've tried Inkscape a few times. Very nice images, but I found that I have become dependent on multi-page documents, so until that happens, it's back to Libreoffice.
Finally, for exact schematics of a PCB design, I suggest you use whatever tool you use for PCB design. I use Altium Summer 2009. I find the schematic entry for this to be way more difficult and slower than LTspice, but it could be possible that the latest Altium is better.