Just sign up to My npower at www.npower.com/mynpower
You'll need your npower account number to hand, so you can set up online services like paperless bills and meter read reminders. You can find your account number at the top right of your npower bill.
If you're having any problems, give our technical team a call on 0845 071 4525 or https://www.npower.com/At_home/applications/MyNpower/CustomerEnquiry.aspx?workflow=CustomerEnquiry