OK, I am a long-time Maya model-builder who has used Photoshop(for a long, long time) and Substance Designer for about as long as it has been in existence, and who has written tutorials for both. So, I'd like to take a crack at answering this question. I'm going to talk about Substance Designer only, not Substance Painter, which is a totally different application - assuming that Substance Designer versus Photoshop is the core of the original question.
A quick answer to the question is that the essential difference between Substance Designer and Photoshop is that Substance Designer produces materials that are "photo-realistic" and will appear to be "photo-realistic" in all "photorealistic rendering engines ("PBR"). In fact, they will have the same appearence in any PBR rendering engine - regardless of the identity of the engine (Corona, Arnold, Maxwell Render, Maverick Render, Octane, etc.). This cannot be said of materials made with Photoshop. Typically, materials made with Photoshop will appear differently in different rendering engines.
Photoshop is essentially an image-based painting program that can produce a wide variety of realistic, stylized or painterly materials - which may or may not be seamless. To use Photoshop, you need to have a basic knowledge of image construction, drawing, painting and manipulation/editing. Substance Designer, on the other hand, is a purely "procedural" - node/graph program in which you create materials by pulling pre-built "nodes" from a library, assembling them and modifying them until you have built up an image of something like tree bark of great depth and detail. Substance Designer materials are generally inherently "seamless."
To use Substance Designer well, you first need to have a reasonable grasp of the basics of computer shader and rendering technology. We are really talking about "light" and the way light interactions with physical materials are handled in computer rendering engines. This fundamental knowledge is not something required by Photoshop. But, in my personal opinion, this basic knowledge about how rendering engines handle light is something all professional model-builders should acquire if they don't already have it. The kind of knowledge I am talking about is best represented by these two papers that can be found here https://substance3d.adobe.com/tutorials/courses/pbrguide And, there are two reasons you want to basic knowledge. One, is to be able to understand how Substance Designer works. The second is because you don't know which rendering engines you will be required to use once you've left school. If you have a basic knowledge of how light and materials are handled in rendering engines, and, therefore, how shaders are made, you will be able to quickly adapt to any modern rendering engine.
Substance Designer is a modern computer technology, with a much more expansive future than Photshop. It is quite good at producing "stylized materials", but its basic purpose is to produce photo-realistic materials for 3D models meant to be physically accurate representations of real or imagined objects. I suppose that in some ways, the focus of Substance Designer is more limited than the focus of Photoshop. However, if your purpose as a 3D model-builder is to produce a model with metals, glass, plastic, wood, ceramic (concrete, porcelain, ceramic, putty, tile), liquid (water, honey, etc.) or translucent (skin, water, thin leaves, flower petals, paper) properties, you can best achieve these with Substance Designer. This is because Substance Designer is making use of the same physics of light mechanisms used by a computer's rendering engines to display the materials as to make them. So, the two are inseparable.
As another overview observation, Photoshop is "old-school" - requiring knowledge and skills in image manipulation, as I said earlier. The functions it performs in 3D model-building can be performed almost equally well by several alternative applications (GIMP, CorelDraw, etc.). Skills in one of these applications are transferable to any of the other similar applications. If you are a student, you should have some of these image manipulation skills, but you might want to learn on one of the cheaper alternatives to Photoshop. [I have Photoshop and use it, but you know what? -- I've come to prefer Coreldraw and CorelPaint for my day-to-day working tools. For most purposes, these tools are quick and more straightforward than Photoshop.)
So, to become a model-builder for the future - especially if you are seeking to become a professional, you need basic image-making skills, and you absolutely must learn and be able to use Substance Designer to construct a variety of basic materials.
At any rate, Photoshop and Substance Designer are not comparable applications. The only thing they have in common is that they both can produce materials that can be part of the shaders for a 3D model.
.......... I'd be happy to answer any more detailed questions about the differences between these two applications. Just ask.