To rewrite your inductive hypothesis:
> If $j\geq 5$ and $j \leq k$, then $j$ cents of postage can be made using only 3-cent and 5-cent stamps.
In the key step you attempt to use the inductive hypothesis for $k-2$. You check that $k-2 \leq k$, but to use the hypothesis you would also need to know $k-2 \geq 5$... which is false when $k=6$.