UPS
Go to this link: https://www.ups.com/upsdeveloperkit?loc=en_US
Click the link half way down the page: Request an access key
Follow all the steps to get your XML Access key.
FedEx
Log in to your FedEx account and follow the FedEx Web Services guide to get your production keys.
Record your Authentication Key, Account Number, and Production Meter Number at the end of your registration process because you need it to activate FedEx in the Shopify admin.
Your Meter Number is emailed to you by FedEx, but the authentication key isn't. Make sure that you record the authentication key before proceeding.
Check for an email from FedEx that includes your Production Password, Account Number, and Production Meter Number.
Canada Post
Login to Canada Post website
Click the green 'Join Now' button, and follow the steps to create a developer profile, the production key information will be waiting at the end.
DHL
Contact your DHL rep for getting your credentials.