Try this page:
help.steampowered.com
People have tried going through this process and got their refund.
steamcommunity.com
Credit to Steam's ShelLuser for the specific process to follow:
Caveats are:
1) Ask for Steam credits, not cash. Just use the credits to buy something else later.
2) Make it clear you haven't played the DLC very many hours, as opposed to the number of hours you played in the base game.
3) Be clear and objective about the problems you encountered - e.g. it's hardware or login issues.
Don't start by being angry. The Steam folks by and large are not aware or responsible for the launch problems.
If you try this path, please report in this thread if it worked for you or if it didn't. This will help others know if it's still a viable path to refund.

Steam Support - Recent Purchases
Log in to your Steam account to get help with your Steam games, contact Steam Support, request refunds, and more. Help is also available if you can't log in, need to reset your password, or recover a hijacked account.
People have tried going through this process and got their refund.

Steam is refusing to refund Odyssey :: Elite Dangerous General Discussions
I made the mistake of pre-ordering the Odyssey DLC, before I looked at the required system specs, which my system does not meet. I was pointed to Frontier's statement that those were the specs for an unoptimized alpha, and would improve by launch. However, the minimum system requirements are...
Credit to Steam's ShelLuser for the specific process to follow:
Go to the overview of your purchases (you can use this link), then select the DLC, then use the option "I still have a question". That will open a ticket about the DLC which will be read by support itself.
Caveats are:
1) Ask for Steam credits, not cash. Just use the credits to buy something else later.
2) Make it clear you haven't played the DLC very many hours, as opposed to the number of hours you played in the base game.
3) Be clear and objective about the problems you encountered - e.g. it's hardware or login issues.
Don't start by being angry. The Steam folks by and large are not aware or responsible for the launch problems.
If you try this path, please report in this thread if it worked for you or if it didn't. This will help others know if it's still a viable path to refund.
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