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What circumstances should I use the 60 degree blade, and does it make much difference?

I tend to use the 45 degree blade for everything except for thick vinyl like reflective vinyl.

I think the 45 degree would still be good for cutting thick vinyl, until it comes to a corner, at this point when it pivots it can give a nasty effect.

I am going to give the two extremes of angle blades as an example:

1) 60 degree - good for cutting thicker material such as reflective vinyl, sandblast rubber etc. Also good for smaller fonts (needs to be done slower).

2) 30 degree - good for thinner vinyl material and larger fonts (can run faster)

The 45 degree blade is the normal in between these.

Explanation:
1) A steeper, angled blade (60°) is tall enough to cut all the way through thick materials and pivots easier when cutting corners.

2) A standard or lower degree blade may not cut thicker materials because the blade gets buried in the material.

Don't forget that you will have to change the offset value on your cutter if you change to a different degree blade.
Normally the manufacturer will have the offset value written on the packaging of the blade.