Eeeerrrr, I think I'll give it a try with words.
Both are used when your trying to find either a side or an angle, but the difference is what the question gives you.
For sine rule, you'll be given either 2 angles and one side - so, you use:
a/sine A = b/sine B
E.g:
You have a triangle (not right angle - if they give you a right angled triangle then just use the trig. ratios), and the question asks you to find the length of side 'AZ'. If the triangle is labelled with another side (say, of length 20 cm) and two angles (let's say, 52 degrees and 63 degrees), and side AZ is opposite one of those angles (let's say that it's oppositte to 52 degrees) then you use sine rule, like this:
AZ/sine 52 = 20/sine 63
Therefore AZ = (20 * sine52)/sine 63.
With me?