Determining who is an extreme user starts with considering what aspect of your design challenge you want to explore to an extreme. List a number of facets to explore within your design space. Then think of people who may be extreme in those facets.
For example, if you are redesigning the grocery store shopping experience you might consider the following aspects: how groceries are gathered, how payment is made, how purchase choices are made, how people get their groceries home, etc. Then to consider the aspect of gathering groceries, for example, you might talk to professional shoppers, someone who uses a shopping cart to gather recyclables (and thus overloads the cart), product pullers for online buyers, people who bring their kids shopping with them, or someone who doesn’t go to grocery stores.
Look for work-arounds (or other extreme behaviors) that can serve as inspiration and uncover insights.