"职员" is more commonly used when it is related to job/occupation.
If you are answering question like "what's your job?", the word "职员" would be more natural to use.
"员工" is more like a wider name for all workers inside a company,
"I work here" -- "我是这里的员工。"
"All members in this company are very excellent." -- "这家公司的员工都非常优秀。"
Base on my personal experience, "职员" is more formal and rarely used in daily talks, but "员工" can be used in any situation.
But as Iris said, their difference is very small.