If you work from home you'll be asked to perform certain tasks generally on a computer. A given job's requirements change depending on whether you're working from home or working conventionally. When you make your choice, be sure to keep an eye on the Career Panel. Choosing the last option takes a vacation day but allows you to do so at the last-second, rather than having to remember to call ahead.
When it's time for the Sim to go to work, you'll be given a pop-up on your phone asking whether you want to work conventionally, work from home, or take time off. All Sims regardless of their neighborhood can join the three new careers.