I would like to use MAMP\'s version of PHP instead of the default installed on my mac. I tried using
ln -s /Applications/MAMP/bin/php5.3/bin/php php <
Well, the 'file exists' error is probably because you attempted to create a sym-link with the name of a file that was already there. I assume you were in the directory containing the php version you were trying to replace or that this was a second attempt and you did not first remove the existing sym-link. I agree with the others with regard to not "replacing/modifying" the default version of php.
Based on the second part of the question, the best way to get around having to type the full path, the answers suggesting an alias are right on point with that. When multiple versions are involved though, that means having to call something other than php to run the version you want to run.
I have a script that lets me "select" the version of php that I would like to work with which then creates a sym-link to that version and lets me simply enter 'php' as my command when I want to use it. I wrote a blog about it here where you can get the script. Based on the answer given by @ioCron I may need to revisit my script to account for the different config folders associated with each version.