General rule of thumb, if its a 'Thai' word, it will always be บ .. if its a sanskrit word, it would normally be ป ภ พ .
Sanskrit words are often more than one syllable.. and u'll probably see other uncommon letters in the spelling - ภ ญ ฎ ธ ฐ ศ ฆ ฤ ษ ณ etc.
There are many books out there in thai about words that thais often spell incorrectly. Pick one up.
I'm sure it will be a good learning aid for u.