My personal suggestion would be to "Know Your Players". I think the 5e rulebook says something to the effect of communicate with your players and ask them what kind of game they're looking to play, but unless they're very familiar with Shadowrun, they're not going to know what they want out of a Shadowrun game. If you've played a game with your group before and you know what they like, then great, but if not, maybe sit around sometime with them before planning out your first Shadowrun session and talk about their experiences with RPGs in the past. If they tell you tales of epic rescues or brutal battles there's a good chance that's what they're going to be comparing your game to, so do your best to fit that in.
I began my GM carreer recently with Shadowrun as well. I've played some RPGs over the years as a player, but even those experiences weren't super extensive. It's going to be a learning process. If you're like me, that first session will be a little painful, especially during combat. Do yourself favor and make sure that you're keeping proper track of where the enemies are located and what everyone's initiative scores are.
As for learning the system, I'm five sessions in (we play once a week, if we're lucky) and I'm still learning. Hell, I feel like I've barely scratched the surface, despite reading the rulebook for 5e from front to back and making notes for every section. Truthfully, until something comes up that you haven't thought out, there's a good chance you're not going to know it. When this happens don't be afraid to tell your players that you're not certain about it, you're going to look into it after the game, but for now let's roll a Skill + Attribute [Limit].
Hope this helps and good luck! It's a great game and an ever better setting. If you're like me and you've enjoyed the setting as a casual fan for a while, you're likely to find playing the game incredibly satisfying.