I guess the only way to really tell weather a substance is amphoteric is to see which reactions it can undergo.
NaHCO3 will become Na+ and HCO3-. The HCO3- can donate H+ which will make NaHCO3 act as an acid. The HCO3- can also accept an H+ making H2CO3, and NaHCO3 will then act as a base.