There are numerous articles on the WWW regarding the advantages of 64-bit environments that can be Googled, perhaps the most relevant article for your specific question is http://www.microsoft.com/sql/editions/64bit/overview.mspx
In short, 32-bit applications are only in danger of failing if they are installed and run directly on the 64-bit hardware itself. If your 32-bit application is running on a 32-bit client computer and is merely connecting to the 64-bit SQL server instance, then everything should be fine.
I have encountered one notable difference between 32-bit and 64-bit SQL server versions when using older Visual Basic connection strings from VBscript files or "classic" ASP pages, in that connections to 64-bit instances require a SQLOLEDB connection:
When connecting to 32-bit versions, it was possible to use this syntax:
Set Db = CreateObject("adodb.Connection")
Db.ConnectionString = "driver={SQL Server};server=<ServerName>;uid=<username>;pwd=<password>;database=<databasename>
The same connection to a 64-bit instance requires a change:
Set Db = CreateObject("adodb.Connection")
Db.ConnectionString = "Provider=SQLOLEDB;server=<ServerName>;uid=<username>;pwd=<password>;database=<databasename>
Hope this helps.