Just because an employee is well-qualified doesn't mean he will take to the new job like a duck to water. Watch for signs of weakness and begin coaching right away on how to solve these problems. Spell out important points about business goals and company dynamics. Have a thorough discussion with your new hire about business goals and corporate culture. Help her nurture her network.
Nobody works in a vacuum.
That's why you should have a frank discussion with your new employee about the individuals who will affect her new job. Be sure to identify direct supervisors, subordinates, major clients and others. Her success will likely hinge on her ability to form a strong business network. Be honest about potential pitfalls and past mistakes. Most organizations are not good at talking about their failures.