The main difference is speed that it changes temperature. So when you turn the hob on it is at the heat you turned it to almost immediately, if you turn it down it is cooler that second.
This won't take long to get used to but if you have recipes which say something along the lines of "Bring to the boil before reducing to a simmer" you can now do exactly that as opposed to the best approximation electric gives.
Another important thing to note is that you want the flames under the pot, not going around the edges: so you need to use the right size pan; usually you want to put it on the largest ring which means the flames are under. If flames do go around the edges you'll find pan handles won't last long and you might have more trouble getting the temperature you want.
You will also find that you have more flexibility with choosing new pans as the thermal contact isn't just at a flat surface: woks, or pans with ribbed or curved surfaces will work better. Pans you might not have liked much before could become new favourites!
You'll love it, I don't think i could ever go back to electric.