Yes, they behave the same when
- there is no 
bar property in foo (not even an inherited one), so a new one is created, or 
- there is a 
bar property that has the writable and configurable attributes set to true 
However, if neither of those is given, the two indeed produce slightly different results.
defineProperty does not consider inherited properties and their descriptors 
- If the existing (possibly inherited) property is an accessor, the assignment will try to call the setter (and fail if none exists), while 
definePropery will overwrite the property with the data descriptor (or fail if it is an own, non-configurable one) 
- If an existing inherited property is a data property, the assignment will fail if 
writable is false, or create a new own property if true, like the defineProperty always does 
- If an existing own property is a data property, the assignment will fail if 
writable is false, or set the new value if true, while defineOwnProperty will fail iff configurable is false and overwrite the attributes otherwise. 
Considering the basic scenario of usage
If by "basic usage" you mean no usage of fancy property attributes, then yes they are equivalent. Yet you should just use the simple assignments, for they are easier to read and faster to execute.
Can we fall back to vanilla in pre-ES6 applications
Notice that full support of defineProperty comes with ES5, so unless you need to consider pre-ES5 (old IE) browsers you wouldn't care at all.