Regarding your examples, "I bought a cup which is similar to the one my brother owns" would imply that you set out to buy a similar cup and you probably would not have bought it if it was not similar.
In "I bought a cup, which is similar to the one my brother owns", the similarity is merely incidental and probably played no part in your purchase decision.
Regarding construction ("syntax"), a native speaker would probably edit the defining version to read, "I bought a cup similar my brother's."
If you had to use "which", then the sentence would be more correct if it read, "I bought a cup which was similar to my brother's." Note the past tense "was", which is necessary if you are using a defining clause. The fact that it was similar at the time of purchase played a vital part in your purchase decision.
English grammar is fascinating. The more you learn, the more there is to learn and enjoy.