There are two ways to get a pickoff at first. One is for your catcher to stand up and fire the ball to the base. Another is for her to throw from her knees. Using minimal footwork will speed the throw.
For a stand up throw, train your catcher to pull back her right foot as she stands, then move through to the left heel as she throws to first. For a knee throw, she needs to pivot her right foot, then drive her momentum forward with the right then left knee as she throws. Avoid locking up the left knee as this will result in a low throw.
To see a demo, watch the video.