Windows networks traditionally rely on passwords for authentication. The problem with passwords is that they are hard to remember. Employees may use the same password for their work login as they do for MySpace, World of Warcraft, and a sketchy adult website membership. Through keyloggers, or fraudulent websites they sign up on, it can be easy for someone to glean a password.
It is for this reason that password security policies are commonly enforced in most Windows networks. These require passwords to meet complexity and length requirements, and force passwords to expire and be replaced after a certain length of time. Forcing your employees to change their passwords frequently opens up another issue. Remember from above that passwords are hard to remember? Well, it's even harder if they get changed every 30 days. In cases like this, many employees will just write their password down. I've even seen someone with their password on a post-it stuck to their monitor. Go Security.
A good way around this, and around many other social networking attempts that may produce a password, is to use two-part authentication. Basicly, in order to login, users will need to provide something they know (like a password) in conjunction with something that they have (token code, thumb print, etc.). If these measures are in effect, the chances of a slipped password compromising your network are all but eliminated.
Beyond physical measures like this, though, the most important defense is education. If you want your employees' help in maintaining security then you need to educate them about what that means. They need to be convinced that security is important, and they need to know what things they need to safeguard. Training sessions and random tests (like calling and claiming you're from tech support and asking for their password) will help to ensure that your network is safe from social engineering.