Train leaves at 6.33 on Hongqiao Train Station.Can I catch that train if I take the first metro on East Nanjing Road?

Actually, the first train of line 2 leaves East Nanjng Road around 05:35 and it arrives at Hongqiao Train Station at 06:07. Therefore, theoretically, you may catch your train.

However, the metro probably delays and upon arrival at the train station, you have to spend time in checking in and finding the platform, so time is so tight. To ensure that you catch the train, it is best to leave earlier.