Guitar cable is shielded cable, which means that there is a core (hot) and a shield (common). Speaker cable, and I'm talking about speaker cable that is used for home stereo etc. is paired wires (in a figure 8 formation) and is unshielded.
The difference is that signal from a guitar is much weaker and more susceptible to interference, while the outputs of an amplifier produce a larger voltage which doesn't pick up as much interference.
But, often you will see speaker cable that is shielded cable like guitar line. I'm not sure if this is a bad thing - I've used shielded cable as outputs to PA bins before.
Short answer is don't use 'speaker' cable (the figure 8 stuff) as a guitar cable.
- gaffa