If you go under benchmarks in the menu, you will find a list of things that accumulate as you web sling across the city. For this trophy, you need to unlock your first combat one which are the benchmarks notated with the green fist icon. The easiest one I have found is called "Take Five" which is for wrapping up 100 enemies with webs. At first it sounded difficult, however you unlock a suit power called "Web Blossom" that leaps you in to the airing webs everything in sight. If you use this in the middle of Fisk Hideouts and thug crimes, you will get quite a few very quickly.