I have never been hired by a startup via a resume.

Not once.

In fact, it is usual years down the line when the HR department is finally officially set up that they ask me to submit my resume so it can complete my file.

What you need to do is "stalk" the company you are interested in. Find out who is there, what positions they have already, what their values are, what kind of people they are (does everyone go out to a bar together after work, or go hiking together on weekends? If that ain't you, wrong company - at least for now.)

Then, figure out what you can offer them and contact them with your plan. Don't ask, tell them how they can't live without you. Offer them a trial period of your services and give them the plan you have to make their company better.

Works every time.