SQL Server will handle all of your multi-user DB access concerns.
Multiple users accessing the same exe from a network location can work but it's kind of a hack. Let's say you wanted to update that exe with a few bug fixes. You would have to ensure that all users close the application before you could release the update. To answer you question though, the application will be isolated to each user running it. You won't have any contention issues when it comes to CRUD operations on the database due to the network deployment.
You might consider something other than a copy/paste style publishing of your application. Visual Studio has a few simple tools you can use to publish your application to a central location using ClickOnce deployment.
http://msdn.microsoft.com/en-us/library/31kztyey(v=vs.110).aspx