Have an interview plan. What is the purpose of the interview? Don't be wishy-washy. Your two questions today could have used a lot more detail.
I do many of these (and am an expert guest) on my blog at http://www.salestactics.org. Here's an example of several: http://www.salestactics.org/sales-expert-interviews/
Write out your questions beforehand. Of course one or two new questions will occur to you while conducting the interview; ask them, too. But have your base set up.
Think about your request from their perspective: WHY would they want to participate? Yes, people want to be cooperative and helpful. But No, they do not want to create content for you (for example, I am asked to be interviewed all the time by people who are compiling such expert interviews to then SELL them...why on earth should I give them content so they can make money with it?!).
So be clear about your purpose.
You really must be looking for expertise, not digging for a job. Fake purpose will be seen through immediately and it will hurt your reputation.
Collecting a series of these interviews online around a specific topic is a great differentiating factor for job hunting, however. This is positioning.
Want to make the most of the interview? Research the company. Find a problem they are having and come to the interview with a solution. Businesses and especially leaders are not looking for another person for the pile they are looking for innovators and solutions. Present them with both and your first interview will be a great one.
I am a big promoter of cold calling leaders in specific industries. Rather than asking leaders for an interview, I recommend calling them to foster a relationship rather than solely for the transactional purpose of getting something from them. By fostering a relationship with the individual, you are more keen to get greater insight from the conversation. This can also lead to additional conversations with other leaders in the space. I would love to speak with you about effective ways to do this!