This is what I do.

New Shooter.

First be aware that most new shooters are slightly intimidated by the gun. 
It is the can hurt you mentality.
Give a brief explanation to allay this fear.

Here is the first time firing process I go thru with new shooters.

“Take your time. Explain, Dry fire, Do Not Rush the first shot”
“Make sure the gun has been made safe.”

Safe Gun:
Start with the smallest gun available.
If a small gun is not available prepare shooter for the recoil of the larger gun.
i.e Make sure they have a firm grip.

Explain and demonstrate how the gun works including the safeties.
Let shooter handle and become familiar with the gun(s)

Semi:
   Rack and release slide –Mag out.
   Rack and release slide Mag in. (Lock back and release.)
   Engage and disengage the safety.
   Inserting and dropping the magazine.
   Dry Fire – Mag out.
   Dry Fire – Mag In

Revolver-Double action:
   Cylinder - Open and close
   Hammer - DA & SA
   Trigger   - DA & SA
   Dry Fire - DA
   Dry Fire - SA
      
Revolver-Single Action
  Cylinder- Open and close the loading gate.
  Hammer.
  Trigger
  Dry Fire

Loaded Gun:
It is important that the shooter place the first shot on the target.

Following all Gun Handling safety rules:

From a distance of two yards.  (Depending on the rules of your range)
Load the gun with one cartridge.
Isosceles position only.
Fire at the target.
Bullet should impact the target.
Some will be in the bullseye.
This makes the shooter feel good about themselves.

Do this a few times with one cartridge.
The wait and additional explanation relaxes the new shooter.   

NOTE:
Most female shooters, due to their smaller frame and body strength,  need a little more
attention paid to the firmness of the grip.

I have been known to change this a little depending on the individual.

You will do just fine.

Be Safe!
JohnC

p.s. Comments Welcome.

You know your wife better than I do.  You might want to listen to the 911 tape on Deadly Force issues.  If you think it's appropriate, knowing your wife, you might want to have her listen and point out the length of time it took for the police to arrive afteer the call was made.  Not to be critical of the police in any way but to point out that things can happen that the police cannot respond to in a timely manner.  Therefore it becomes incumbent on us to be responsible for our own self defense. 

Doc,
do you think this is a good idea?

JMOfartO:

"Vanity, thy name is woman",

Just get her a pistol of her own with her name on it...

Jesse

I have owned for a few years, but she never really had an interest, but only tolerated the idea.  Then some home invasions in the area that led to the inevitable self defense thoughts.  She read an article I printed off from jpfo.org.  She finally asked about guns, gun safety and whether or not she should learn to shoot...

So, I unloaded, checked and rechecked the handgun and let her hold it.  I let her know about muzzle control and finger off the trigger safety stuff but in a non-condescending way I hope!  She manipulated the slide, inserted and removed the mag, holstering, etc.  We dry practiced.  She became familiar with it and unafraid of it after a few days.

We visited a local range and watched people of all sorts shoot and we talked about what we saw that was "good" or "bad" in regard to safely handling a weapon.  We left and went out to eat and it ended up being a nice date night!  We talked about it a few more days, and then...

THEN we went to the range!  She had fun.  We went back the very next weekend.  She was becoming a gun person, and hopefully a safe one.  I still wanted her to know how serious self defense was and get good training.  Well, as a member of Front Site and having a "Free for a 1st Timer" certificate, yup we both went to Front Site!  She doesn't even blink now when I remove a weapon from the holster and put it on the night stand or visa-versa in the morning, and she is no longer uneasy about it.   

She likes the way my AR looks and wants to shoot it.  Jeeminy-Christmas, life is good. 

Nice to know that if I'm face down and being beaten (or insert whatever scenario comes to mind here) she'll have at least a better chance of saving her life and maybe mine than she had before!  Isn't that why we do this?