There are tons of spice circuits all over the internet. As far as learning, here is a good link to get you started.
http://www.simonbramble.co.uk/lt_spice/ltspice_lt_spice.htmJust try a simple circuit, maybe a low pass filter. Once you start getting the hang of creating and editing components, you can gradually go to more complicated circuits with transistors, fets, and op amps.
For pedal building, you can use LTSpice two ways:
(1) Create the circuits and use an unsteady voltage source (e.g. 0.1V amplitude sine wave at 800 hz) to represent your guitar signal. What is fascinating is to observe how the simple sine wave is distorted by an overdrive or fuzz circuit at the output. Often you can tell what kind of sound you'll get simply by looking at the waveform (it's like having a virtual o-scope).
(2) Perform a frequency sweep to look at the response resulting from a sine wave signal at the input. The frequencies of interest for pedals typically range from 50 Hz to 10,000 Hz. This analysis can show you if which frequencies will be accentuated, and is particularly instructive for tuning tone stacks and other filter elements in the circuit.
Some examples of these kinds of plots can be found at the Electrosmash site (tubescreamer example):
http://www.electrosmash.com/tube-screamer-analysis