The number 1 most important thing for you to focus on as a founder or CEO of a startup is going to keep shifting over the life of the company.
If things go well while you have the title of "CEO" you may go from coder -> lead recruiter -> eng manager / product manager -> sales guy -> CMO -> acting VP product -> acting VP sales -> external evangelist -> government relations lead -> Global Tech Statesman -> Gubanatorial candidate -> Pundit -> retired old cranky guy who always complains about how much stronger entrepreneurs were "back in my day when YC only admitted 42 startups a batch".
Startups are a rollercoaster ride - every time you make it over one hump (hiring the first employee, fundraising, launching an alpha, etc.) you will suddenly see the next, new challenge looming on the horizon. You need to stay focused on the challenge.
As a founder or CEO, you should be constantly asking yourself what is the single more important thing you should be doing for the company at any given period of time. And then you should focus most of your time on that. A good exercise to try:
Once a week, take a step back and ask yourself what you are trying to accomplish, and what are the 1-2 most important things that will get you there.
Every morning, make a list of the 1-3 things you absolutely need to get done that day.
Get those things done.
Don't get distracted by the easy low hanging fruit that doesn't matter - it just wastes your time even if you get satisfaction by doing it.
In parallel to the spot roles you are playing (e.g. CMO, VP sales, whatever), the two most consistently important jobs for the CEO of a startup on an ongoing basis are:
1. Make sure you do not run out of money. People seem to forget that running out of money is the #1 reasons startups fail.
2. Hiring and firing. As CEO, you constantly need to be hiring the best possible people, and letting underperformers go.
Larry Page of Google is a great example of someone who throughout his career at Google has focused on #2 (well, at least the hiring part). When I was at Google, each job candidate used to have to go through at least 8 interviews - and they all had to result in "hires" from the interviewers. Any "no hires" and the person would not advance. Additionally, Larry would read the feedback package, grades, college transcript etc. of literally EVERY SINGLE hire that Google hired. I have heard of him blocking the hiring of people who e.g. got a "B" in a class he deemed to be an easy one.
I am sure this prevented some great people from getting hired at Google, but I bet it also kept out an even larger number of bozos.
This post was inspired by a conversation with Hiten Shah, who has some great ideas on this area.
Some past hiring posts:
Hiring the First 5 Engineers: What Sorts of People Do You Want On Your Team?
Hiring Tip: Graph Interview Performance vs Years of Experience to Spot Outliers
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