I am a help dek analyst and looking to start taking classes toward technical certifications(MCSE, CNE, etc.). Am I better off writing the tuition expenses off on taxes or taking a tuition reimbursement from my employer? Do tuition reimbursments get taxed?

These are job related and would be tax deductible on your tax return, but they would be subject to the 2% of AGI limitation so you don't get the full deduction. Also, you'd be paying for it. having your employer pay for it doesn't cost you anything and he gets the full deduction.
See IRS Publication 17. It has a lot of information on filing personal returns.