Give 'em a 'sandbox' run through Food Fight or the equivalent, and let them tweak their characters after. I regret not having been able to do that with my first-ever character in SR.
If possible, get a good look at the character sheets before the first game, and write up 'cheat sheets' on rules that come into play. Bob the Sammy has a full-auto weapon? Note down the various dicepool mods for burst and full auto fire. A copy of the mage's spell descriptions are handy, too.
I highly suggest that players bring their own cheatsheets as well; I usually write up a new one for each character listing abilities, and a list of common rolls/dice pools. It is good to be able to glance at the back of my character sheet and know that the 'standard' dice pool for her pistol is 13.
On that thought, you might want to do similar for the NPCs. Each player has just a single character (aside from drones or spirits); you have an entire world to play! Making combat go faster allows more fun story/RP time.
1. I fell in love with Shadowrun simply by going through the character creation process and that was also what I saw with those that we converted. The complexity of various system rules were actually the offputting thing, although a certain type of player took to the high chance of death. They were typical gamers and familiar with fantasy and sci though.
I agree with the idea to run them through a sandbox run or two to get used to it. I'd suggest purchasing the 1st edition version of Sprawl Sites. I saw someone suggest it on these boards and bought it recently online for 4 bucks. The mechanics need converted to other editions, but I found it of great value and it would be of even greater value to someone trying to ease new players into the SR universe. There's a large array of encounters and mini adventures. There's also some great maps, which I find very useful as it usually is the hardest part for me and just having a map inspires me to create adventures. It has other useful things too, like some contacts, but the maps and the encounters/mini adventures are the real gems.
There is also a 4th edition Sprawl Sites just put out, but I haven't checked it out yet. Based on the quality of the 1st edition, I will likely pick it up soon.
Something that worked well with me easing new players into Shadowrun was to run early campaigns with limited systems. What I mean by that is to start you eliminate certain aspects of Shadowrun, preferably the ones with more difficult and complex rules. So, typically, we'd eliminate things like deckiing and vehicle combat. Players could drive cars of course, we simply didn't create combat situations while driving. Any decking would be done by npcs and just given some result or perhaps a very simple single dice test would determine results.
We might also eliminate magic or limit it to npcs. We did alot of just having the characters go around killing gangers and doing simple breaking and entering, shoot em up jobs. We generally included the skill system as well, so there was things going on like electronics to open a maglock and negotiation to fast talk the security guard. Once some of us were comfortable enough with the magic system, we added that and let pcs by mages and shamans. Much later on we added vehicle combat. Years later only a few of us are familiar with the decking system and players rarely play deckers. (We don't ban it)
I also agree with the idea for cheat sheets for difficult rules and npc stats. Once I started creating sheets on notecards, my combats speeded up dramatically. Another thing I found sped up combat was rolling dice out in the open on the table, rather than behind a GM screen. (A habit from my AD&D days)