I think the best way is to understand your long time goal for your start up . And understanding who and how can your team help you achieve that goal .
As a HR manager myself i try to look for certain personality types and roles that these people can fill in . So as an early stage start up you need to understand that there 5 types of people you will definitely need.
1 - The Dreamer - The person with all the ideas and clear way to execute that
2- The Lead Generator - The person who will be making the sales funnel filled with potential leads and making the brand visible to potential clients
3 - The Closer - the person who is a master negotiator and who will close the potential leads
4 - The Product Expert - The person who knows the product inside out and knows how to improvise when something goes wrong
5 - Client Service - Person who can manage queries from clients and give the best service .
Here s a link to article Im referring to so that you can understand how to get there - http://quikchex.in/people-b2b-startup-hire/