Congrats, scrappy startup phase is exciting, lots of opportunity to make a big impact!
I suggest starting by getting a baseline understanding of their sales cycle today. What has their approach been? Where are they seeing success, and where are they bottlenecked? Your focus should be different if they're not able to get in the door (help them with ICP insights and positioning for outbound targeting!) vs. struggle to get from first call to pitch (work on discovery questions!).
As you go through the sales cycle with the team, "feed two birds with one scone" by mining for customer stories among the wins they've landed. Package those up into callouts for outbound emails!
Given you asked about process, I'd focus on a regular cadence of connection between you and the sales team to build a relationship and shared understanding of priorities in an ongoing manner. Use that time to learn what the latest experiments have been, and how you can build on what they're seeing works.