When you install a licensed managed package in your organization from AppExchange, you purchase a certain number of licenses from the package developer or publisher. You can assign each license to a user within your organization. If you assign all available licenses, but would like to grant licenses to additional users, you can reassign a license or purchase more.
Users with a Checkout account can add licenses for your organization. If your organization doesn’t have self-service access to Checkout, submit a request to your salesforce.com representative. To add more licenses, you must create a quote using Checkout. For more detailed instructions on creating a quote, see the Force.com help.
Navigate to Appropriate Location in System Setup

- Click on your name on right side of an application.
- Click on Setup.
In Setup page scroll down to Checkout and click on Checkout Summary
In Setup page scroll down to Checkout and click on Checkout Summary.

Checkout Summary

On Checkout Summary page, Click on Proceed to Checkout.
Back to Administration Setup

Click Your Name | Setup | Company Profile | Company Information. Company Information detail page will open.
Verify Licenses

click Buy More Licenses in the related list of Company Information to add the licenses, for more information see Force.com help.