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Build something that people want and make it grow and things have a way of working out. Many VC firms actively monitor the top of app stores, angellist and ask what software their friends and portfolio companies are using. Build something awesome and people--including investors--will find a way to connect with you.

There are benefits of working at another startup first: gained skills, experience and network. If you want to go right away into starting a startup it'll take some combination of increased hustle and more solid proof/the company being further along before raising a seed round.

Many investors also regularly check app store rankings, angellist, accelerator demo days and ask their friends and portfolio companies about "what is interesting?" or some version of that question. Build something interesting/awesome and word can spread across silicon valley very quickly.